(Meth)acryloyl-terminated polyisobutylene polymer, method for producing the same, and active energy ray-curable composition

ABSTRACT

The purpose of the present invention is to provide a polymer having a low halogen atom content remaining in the polymer, a simple production method thereof, an active energy ray-curable composition that can be rapidly cured by an irradiation of a small amount of light, and a cured product thereof. These purpose can be achieved by an active energy ray-curable composition, including a polyisobutylene polymer (A) represented by the following general formula (1) (wherein R 1  represents a monovalent or polyvalent aromatic hydrocarbon group, or a monovalent or a polyvalent aliphatic hydrocarbon group; A represents a polyisobutylene polymer; R 2  represents a divalent saturated hydrocarbon group having 2-6 carbon atoms, which contains no hetero atoms; R 3  and R 4  each represent hydrogen, a monovalent hydrocarbon group having 1-20 carbon atoms, or an alkoxy group having 1-20 carbon atoms; R 5  represents hydrogen or a methyl group; and n denotes a natural number), and an active energy ray polymerization initiator (B).

TECHNICAL FIELD

The present invention relates to a polymer having a low halogen atomcontent remaining in the polymer, a simple production method thereof, anactive energy ray-curable composition that can be rapidly cured by anirradiation of a small amount of light, and a cured product thereof.

BACKGROUND ART

Techniques for crosslinking resins with active energy rays such as UV(ultraviolet rays) or EB (electron beam) are widely known. Situations inwhich such techniques are utilized instead of conventional curingreactions triggered by heat have been increasing.

Active energy ray-curing techniques have improved productivity whencompared to thermosetting techniques, due to requirement of lesssolvent, less energy, and less space in the curing process as well as anability to complete the reaction in a short time in general. Inaddition, since light can be irradiated uniformly on a substrate havinga complex shape, an active energy ray-curing technique has the benefitthat it is easy to achieve higher functionality. These techniques arethus used in applications such as inks, paints, adhesives, sealingmaterials, electrical and electronic precision components, moldedarticles and the like.

Some of the major characteristics required for resins in theabove-described fields include durability, heat resistance,weatherability, water resistance, permeability of moisture and gas, andthe like. An example of a resin which has a combination of suchcharacteristics is a polyisobutylene polymer.

The (meth)acryloyl-terminated polyisobutylene described in PatentLiterature 1 is known as a resin having a photocrosslinkable group on apolyisobutylene end. In the technique disclosed in Patent Literature 1,the synthesis pathway of the (meth)acryloyl-terminated polyisobutyleneis an extremely long linear synthesis method, and the chlorine atomsthat inherently remain in the obtained resin may be undesirabledepending on the application.

Patent Literature 2 discloses a technique relating to a(meth)acryloyl-terminated polyisobutylene polymer that essentially doesnot contain halogen atoms. However, the disclosed synthesis method iscomplex, and the silane compound and platinum catalyst required forsynthesis are very expensive. Therefore, there were large economiclimitations to industrial production. Further, this method requires anirradiation of light in an amount of as large as 2,000 J to cure theobtained curable composition. Accordingly, there is a need for a polymerthat can be synthesized more simply and that can be cured by anirradiation of a small amount of light.

Patent Literature 3 discloses a technique that functionalizes apolyisobutylene terminal with a phenoxy derivative. However, there areno specific examples showing the presence of the polymer withunhydrolyzed terminals under a condition wherein a compound having aphenoxy group and a (meth)acryloyl ester group is used as an end capagent and a Lewis acid coexists during a reaction and a post-treatment.Moreover, it is unclear whether the obtained polymer is actually curedwith active energy rays, and further, the activity of this polymer isalso unclear.

Patent Literature 4 discloses a technique that introduces an alkenylgroup onto an isobutylene polymer end by a Friedel-Crafts reaction.Patent Literature 4 only describes that this alkenyl-terminatedpolyisobutylene polymer can be cured by forming a bond by ahydrosilylation reaction with a hydrosilane compound in the presence ofa platinum catalyst.

CITATION LIST Patent Literature

-   Patent Literature 1: JP 2001-31714 A-   Patent Literature 2: JP 10-87726 A-   Patent Literature 3: WO 2010/083181-   Patent Literature 4: JP 05-186513 A

SUMMARY OF INVENTION Technical Problem

It is an object of the present invention, which was created inconsideration of the above-described problems, to provide a polymerhaving a low halogen atom content remaining in the polymer, a simpleproduction method thereof, an active energy ray-curable composition thatcan be rapidly cured by an irradiation of a small amount of light, and acured product thereof.

Solution to Problem

As a result of diligent research into achieving the above object, thepresent inventors found that the above-described problems can be solvedby combining a (meth)acryloyl-terminated polyisobutylene polymerrepresented by the following general formula (1), a(meth)acryloyl-terminated polyisobutylene polymer, and an active energyray polymerization initiator, thereby completing the present invention.

Namely, the present invention relates to an active energy ray-curablecomposition comprising: a (meth)acryloyl-terminated polyisobutylenepolymer (A) represented by the following general formula (1):

wherein R¹ represents a monovalent or polyvalent aromatic hydrocarbongroup, or a monovalent or a polyvalent aliphatic hydrocarbon group; Arepresents a polyisobutylene polymer; R² represents a divalent saturatedhydrocarbon group having 2 to 6 carbon atoms, which contains no heteroatoms; R³ and R⁴ each represent hydrogen, a monovalent hydrocarbon grouphaving 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbonatoms; R⁵ represents hydrogen or a methyl group; and n denotes a naturalnumber; and

an active energy ray polymerization initiator (B).

It is preferable that a main chain of the polyisobutylene polymerrepresented by A be produced by living cationic polymerization.

It is preferable that the (meth)acryloyl-terminated polyisobutylenepolymer (A) have a molecular weight of 200 to 500,000 in terms of numberaverage molecular weight based on polystyrene measured by size exclusionchromatography, and a molecular weight distribution of 1.8 or less.

It is preferable that a content of the active energy ray polymerizationinitiator (B) be 0.001 to 20 parts by weight per 100 parts by weight ofthe (meth)acryloyl-terminated polyisobutylene polymer (A).

The present invention also relates to a cured product obtainable bycuring the above-described active energy ray-curable composition withactive energy rays.

The present invention also relates to a (meth)acryloyl-terminatedpolyisobutylene polymer (A) represented by the following general formula(1):

wherein R¹ represents a monovalent or polyvalent aromatic hydrocarbongroup, or a monovalent or a polyvalent aliphatic hydrocarbon group; Arepresents a polyisobutylene polymer; R² represents a divalent saturatedhydrocarbon group having 2 to 6 carbon atoms, which contains no heteroatoms; R³ and R⁴ each represent hydrogen, a monovalent hydrocarbon grouphaving 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbonatoms; R⁵ represents hydrogen or a methyl group; and n denotes a naturalnumber.

It is preferable that R² represent a divalent hydrocarbon group selectedfrom the group consisting of —CH₂CH₂—, —CH₂CH₂CH₂—, —CH₂CH₂CH₂CH₂—,—CH₂CH₂CH₂CH₂CH₂—, and —CH₂CH₂CH₂CH₂CH₂CH₂—. It is more preferable thatR² represent —CH₂CH₂—.

It is preferable that R³ and R⁴ represent hydrogen.

It is preferable that R⁵ represent hydrogen.

It is preferable that the (meth)acryloyl-terminated polyisobutylenepolymer (A) have a molecular weight of 200 to 500,000 in terms of numberaverage molecular weight based on polystyrene measured by size exclusionchromatography (SEC), and a molecular weight distribution (a valuerepresented by Mw/Mn which is a ratio of the weight average molecularweight Mw to the number average molecular weight Mn) of 1.8 or less.

The present invention also relates to a method for producing a(meth)acryloyl-terminated polyisobutylene polymer (A) represented by thefollowing general formula (1):

wherein R¹ represents a monovalent or polyvalent aromatic hydrocarbongroup, or a monovalent or a polyvalent aliphatic hydrocarbon group; Arepresents a polyisobutylene polymer; R² represents a divalent saturatedhydrocarbon group having 2 to 6 carbon atoms, which contains no heteroatoms; R³ and R⁴ each represent hydrogen, a monovalent hydrocarbon grouphaving 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbonatoms; R⁵ represents hydrogen or a methyl group; and n denotes a naturalnumber,

comprising reacting a halogen-terminated polyisobutylene polymer (a1)obtainable by cationic polymerization and a compound (a2) having a(meth)acryloyl group and a phenoxy group in the presence of a Lewis acidcatalyst.

It is preferable that the cationic polymerization be living cationicpolymerization.

It is preferable that the compound (a2) having a (meth)acryloyl groupand a phenoxy group be 2-phenoxyethyl acrylate.

It is preferable that the halogen-terminated polyisobutylene polymer(a1) and the compound (a2) having a (meth)acryloyl group and a phenoxygroup be reacted under a temperature condition of less than 0° C.

It is preferable that the halogen-terminated polyisobutylene polymer(a1) and the compound (a2) having a (meth)acryloyl group and a phenoxygroup be reacted under a reaction condition in which a molar ratio ofthe compound (a2) having a (meth)acryloyl group and a phenoxy group tothe Lewis acid (a value represented by (number of moles of compound (a2)having a (meth)acryloyl group and a phenoxy group)/(number of moles ofLewis acid)) is less than 1.0.

Advantageous Effects of Invention

According to the (meth)acryloyl-terminated polyisobutylene polymeraccording to the present invention, a polymer having a very low halogenatom content remaining in the polymer can be produced more simply than aconventional production method. Further, a composition including such apolymer can be rapidly cured by an irradiation of a small amount oflight.

DESCRIPTION OF EMBODIMENTS

The polyisobutylene polymer (A) according to the present invention isrepresented by the following general formula (1):

wherein R¹ represents a monovalent or polyvalent aromatic hydrocarbongroup, or a monovalent or a polyvalent aliphatic hydrocarbon group; Arepresents a polyisobutylene polymer; R² represents a divalent saturatedhydrocarbon group having 2 to 6 carbon atoms, which contains no heteroatoms; R³ and R⁴ each represent hydrogen, a monovalent hydrocarbon grouphaving 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbonatoms; R⁵ represents hydrogen or a methyl group; and n denotes a naturalnumber.

The moiety A in the (meth)acryloyl-terminated polyisobutylene polymer(A) according to the present invention is a polyisobutylene polymer.However, in addition to isobutylene mainly used as the monomer formingthis polyisobutylene polymer, other cationically polymerizable monomersmay also be copolymerized as long as the effects of the presentinvention are not impaired.

Examples of such a monomer include olefins having 4 to 12 carbon atoms,vinyl ethers, aromatic vinyl compounds, vinyl silanes, allylsilanes andthe like. Specific examples thereof include isoprene, amylene,1,3-butadiene, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene,pentene, 4-methyl-1-pentene, hexene, vinyl cyclohexene, α-pinene,β-pinene, limonene, styrene, indene, α-methylstyrene, methoxystyrene,methylstyrene, trimethylstyrene, chlorostyrene, dichlorostyrene, methylvinyl ether, ethyl vinyl ether, isobutyl vinyl ether,vinyltrichlorosilane, vinylmethyldichlorosilane,vinyldimethylchlorosilane, vinyldimethylmethoxysilane,vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane,divinyldimethylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane,trivinylmethylsilane, tetravinylsilane, allyltrichlorosilane,allylmethyldichlorosilane, allyldimethylchlorosilane,allyldimethylmethoxysilane, allyltrimethylsilane, diallyldichlorosilane,diallyldimethoxysilane, diallyldimethylsilane and the like.

When using another monomer that is copolymerizable with isobutylene, thecontent of that monomer in the isobutylene polymer is preferably in therange of 50% by weight or less, more preferably 30% by weight or less,and even more preferably 10% by weight or less.

R¹ in the above general formula (1) represents a monovalent orpolyvalent aromatic hydrocarbon group, or a monovalent or a polyvalentaliphatic hydrocarbon group. Specific examples of the aromatichydrocarbon group include a cumyl group, an m-dicumyl group, a p-dicumylgroup, a 5-tert-butyl-1,3-dicumyl group, a 5-methyl-1,3-dicumyl group, a1,3,5-tricumyl group and the like. On the other hand, specificallypreferred examples of the aliphatic hydrocarbon group include a grouprepresented by CH₃ (CH₃)₂CCH₂ (CH₃)₂C— and —(CH₃)₂CCH₂(CH₃)₂CCH₂(CH₃)₂C—. Among these, from the perspective of availability, acumyl group, an m-dicumyl group, a p-dicumyl group, a5-tert-butyl-1,3-dicumyl group, CH₃(CH₃)₂CCH₂(CH₃)₂C—, and—(CH₃)₂CCH₂(CH₃)₂CCH₂(CH₃)₂C— are especially preferable.

R² in the above general formula (1) represents a divalent saturatedhydrocarbon group having 2 to 6 carbon atoms, which contains no heteroatoms. Specifically preferred examples thereof include —CH₂CH₂—,—CH₂CH₂CH₂—, —CH₂CH₂CH₂CH₂—, —CH₂CH₂CH₂CH₂CH₂—, —CH₂CH₂CH₂CH₂CH₂CH₂— andthe like. Among these, from the perspective of availability, —CH₂CH₂— ispreferable.

R³ and R⁴ in the above general formula (1) each represent hydrogen, amonovalent hydrocarbon group having 1 to 20 carbon atoms, or an alkoxygroup having 1 to 20 carbon atoms. Specific examples thereof include amethyl group, an ethyl group, a propyl group, an isopropyl group, abutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, anisopentyl group, a neopentyl group, a hexyl group, an isohexyl group, aneohexyl group, a heptyl group, an octyl group, an isooctyl group, asec-octyl group, a tert-octyl group, a 2-ethylhexyl group, a nonylgroup, a decanyl group, a methoxy group, an ethoxy group, a propoxygroup, an isopropoxy group, a butoxy group, a sec-butoxy group, atert-butoxy group, a pentyloxy group, an isopentyloxy group, aneopentyloxy group, a hexyloxy group, an isohexyloxy group, aneohexyloxy group, a heptyloxy group, an octyloxy group, an isooctyloxygroup, a sec-octyloxy group, a tert-octyloxy group, a 2-ethylhexyloxygroup, a nonyloxy group, a decanyloxy group and the like.

Among these, from the perspectives of availability and reactivity,hydrogen is preferable.

R⁵ in the above general formula (1) represents hydrogen or a methylgroup. From the perspectives of availability and reactivity, hydrogen ispreferable.

In the above general formula (1), n denotes a natural number. In orderto achieve a sufficient strength, durability, gel fraction and the likewhen obtaining a crosslinkable macromolecule by a crosslinking reaction,n is preferably 2 or 3.

The molecular weight of the (meth)acryloyl-terminated polyisobutylenepolymer (A) according to the present invention is not especiallylimited. However, from perspectives such as fluidity, and post-curingphysical properties, the number average molecular weight based on a SEC(size exclusion chromatography) measurement is preferably 200 to500,000, more preferably 300 to 500,000, and even more preferably 1,000to 500,000.

If the number average molecular weight of the (meth)acryloyl-terminatedpolyisobutylene polymer (A) is lower than 200, the degree of curabilityof the active energy ray-curable composition is too high, which is notdesirable. On the other hand, if the number average molecular weight ismore than 500,000, fluidity and workability tend to deteriorate.

In addition, from the perspective of processing stability, the molecularweight distribution (a value represented by (weight average molecularweight Mw)/(number average molecular weight Mn)) of the(meth)acryloyl-terminated polyisobutylene polymer (A) is preferably 1.8or less, more preferably 1.5 or less, and even more preferably 1.3 orless.

It is preferable that the (meth)acryloyl-terminated polyisobutylenepolymer (A) represented by general formula (1) according to the presentinvention be obtained in one stage by a reaction between ahalogen-terminated polyisobutylene polymer (a1) and a compound (a2)having a (meth)acryloyl group and a phenoxy group.

It is preferable that the halogen-terminated polyisobutylene polymer(a1) be represented by the following general formula (I):R¹(-A-X)_(n)  (I)

wherein X represents a halogen atom and R¹ and n are the same asdescribed above.

X in the above general formula (I) represents chlorine, bromine, oriodine. From the perspectives of availability and compound stability,chlorine is preferable.

The method for producing the halogen-terminated polyisobutylene polymer(a1) is preferably cationic polymerization, and more preferably livingcationic polymerization.

Details of the living cationic polymerization that can be applied in thepresent invention can be found in, for example, the descriptions aboutsynthesis reactions in a book by J. P. Kennedy et al. (CarbocationicPolymerization, John Wiley & Sons, 1982) and in a book by K.Matyjaszewski et al. (Cationic Polymerizations, Marcel Dekker, 1996).

Specifically, the halogen-terminated polyisobutylene polymer (a1) can beobtained by polymerizing a monomer component that mainly includesisobutylene in the presence of a compound represented by the followinggeneral formula (II), which is a polymerization initiator:R¹Xn  (II)

wherein X and n are the same as described above.

It is thought that the compound represented by the above general formula(II) acts as a polymerization initiator, and that carbocations areproduced in the presence of a Lewis acid and the like, which serve as astarting point for cationic polymerization.

Examples of the compound of general formula (II) used in the presentinvention include the following compounds:

(1-chloro-1-methylethyl)benzene [C₆H₅C(CH₃)₂Cl];1,4-bis(1-chloro-1-methylethyl)benzene [1,4-Cl(CH₃)₂CC₆H₄C(CH₃)₂Cl];1,3-bis(1-chloro-1-methylethyl)benzene [1,3-Cl(CH₃)₂CC₆H₄C(CH₃)₂Cl];1,3,5-tris(1-chloro-1-methylethyl)benzene [1,3,5-(ClC(CH₃)₂)₃C₆H₃]; and1,3-bis(1-chloro-1-methylethyl)-5-(tert-butyl)benzene[1,3-(C(CH₃)₂Cl)₂-5-(C(CH₃)₃)C₆H₃].

Among these, 1,4-bis(1-chloro-1-methylethyl)benzene and1,3,5-tris(1-chloro-1-methylethyl)benzene are especially preferable.

(1-Chloro-1-methylethyl)benzene is also called cumyl chloride.Bis(1-chloro-1-methylethyl)benzene is also calledbis(α-chloroisopropyl)benzene, bis(2-chloro-2-propyl)benzene, or dicumylchloride. Tris(1-chloro-1-methylethyl)benzene is also calledtris(α-chloroisopropyl)benzene, tris(2-chloro-2-propyl)benzene, ortricumyl chloride.

When producing the halogen-terminated polyisobutylene polymer (a1), itis preferable that a Lewis acid catalyst coexist. Such a Lewis acid maybe any Lewis acid that can be used in cationic polymerization. Examplesof acids that can be preferably used include metallic halides such asTiCl₄, TiBr₄, BCl₃, BF₃, BF₃.OEt₂, SnCl₄, SnBr₄, SbCl₅, SbBr₅, SbF₅,WCl₆, TaCl₅, VCl₅, FeCl₃, FeBr₃, ZnCl₂, ZnBr₂, AlCl₃, and AlBr₃; andorganometallic halides such as Et₂AlCl, Me₂AlCl, EtAlCl₂, MeAlCl₂,Et₂AlBr, Me₂AlBr, EtAlBr₂, MeAlBr₂, Et_(1.5)AlCl_(1.5),Me_(1.5)AlCl_(1.5), Et_(1.5)AlBr_(1.5), and Me_(1.5)AlBr_(1.5). Amongthese, when considering catalytic capability and ease of industrialavailability, TiCl₄, BCl₃, and SnCl₄ are preferable, and in terms of abalance between catalytic activity and availability, TiCl₄ is especiallypreferable in the present invention.

The amount of use of the Lewis acid is not especially limited, and canbe set based on the polymerization properties of the monomers to beused, the polymerization concentration or the like. Usually, the Lewisacid can be used in an amount in the range of 0.01 to 300 molarequivalents relative to the compound represented by general formula(II), and preferably in the range of 0.05 to 200 molar equivalents.

During production of the halogen-terminated polyisobutylene polymer(a1), an electron donor component can optionally also be made present.It is thought that this electron donor component has the effect ofstabilizing the growing carbocation during cationic polymerization.Addition of an electron donor allows production of a polymer having anarrower molecular weight distribution and a controlled structure.Although compounds that can be used as the electron donor component arenot especially limited, examples thereof include pyridines, amines,amides, sulfoxides, esters, metal compounds having an oxygen atom bondedto a metal atom or the like.

Specific examples of the above-described electron donor component whichcan be used may typically include, as compounds having a donor numberdefined as a parameter representing the strength as an electron donorfor various compounds of 15 to 60, 2,6-di-t-butylpyridine,2-t-butylpyridine, 2,4,6-trimethylpyridine, 2,6-dimethylpyridine,2-methylpyridine, pyridine, diethylamine, trimethylamine, triethylamine,tributylamine, N,N-dimethylaniline, N,N-dimethylformamide,N,N-dimethylacetamide, N,N-diethylacetamide, dimethyl sulfoxide, diethylether, methyl acetate, ethyl acetate, trimethyl phosphate,hexamethylphosphoric triamide, titanium alkoxides such as titanium(III)methoxide, titanium(IV) methoxide, titanium(IV) isopropoxide andtitanium(IV) butoxide; and aluminum alkoxides such as aluminumtriethoxide and aluminum tributoxide. Preferable examples include2,6-di-t-butylpyridine, 2,6-dimethylpyridine, 2-methylpyridine,pyridine, diethylamine, trimethylamine, triethylamine,N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide,titanium(IV) isopropoxide, titanium(IV) butoxide and the like. The donornumber of the various substances described above is illustrated in “TheDonor-Acceptor Approach to Molecular Interactions”, Gutmann, translatedby Otaki and Okada, Gakkai Shuppan Center (1983). Among thesesubstances, 2-methylpyridine, which has a notable addition effect, isespecially preferable.

The above-described electron donor component is used, usually, in anamount that is 0.01 to 50 times, and preferably in the range of 0.1 to30 times, the number of moles of the above-described polymerizationinitiator.

Polymerization of the halogen-terminated polyisobutylene polymer (a1)can be carried out in an organic solvent if necessary. This organicsolvent is not especially limited, as long as it does not substantiallyinhibit the cationic polymerization. Specific examples thereof includehalogenated hydrocarbons such as methyl chloride, dichloromethane,chloroform, ethyl chloride, dichloroethane, n-propyl chloride, n-butylchloride, and chlorobenzene; alkylbenzenes such as benzene, toluene,xylene, ethylbenzene, propylbenzene, and butylbenzene; straight-chainaliphatic hydrocarbons such as ethane, propane, butane, pentane, hexane,heptane, octane, nonane, and decane; branched-chain aliphatichydrocarbons such as 2-methylpropane, 2-methylbutane,2,3,3-trimethylpentane, and 2,2,5-trimethylhexane; alicyclichydrocarbons such as cyclohexane, methylcyclohexane, andethylcyclohexane; paraffin oil produced by hydrogenating and refiningpetroleum fractions and the like.

In consideration of the balance between, for example, the polymerizationproperties of the monomers forming the isobutylene polymer and thesolubility of the produced polymer, these solvents can be used alone orin combination of two or more thereof. The amount of the solvent to beused is determined so that the concentration of the polymer is 1 to 50%by weight, and preferably 5 to 35% by weight, in consideration of theviscosity of the obtained polymer solution and how easily heat isremoved.

During the actual polymerization, the respective components are mixedunder cooling, for example, at a temperature of at least −100° C. andless than 0° C. From the viewpoint of balance between energy costs withpolymerization stability, an especially preferable temperature range is−30° C. to −80° C.

The compound (a2) having a (meth)acryloyl group and a phenoxy group ispreferably represented by general formula (2):

wherein R², R³, R⁴, and R⁵ are the same as above.

Specific examples thereof may include 2-phenoxyethyl acrylate,3-phenoxypropyl acrylate, 4-phenoxybutyl acrylate, 5-phenoxypentylacrylate, 6-phenoxyhexyl acrylate, 2-phenoxyethyl methacrylate,3-phenoxypropyl methacrylate, 4-phenoxybutyl methacrylate,5-phenoxypentyl methacrylate, 6-phenoxyhexyl methacrylate,2-(2-methylphenoxy)ethyl acrylate, 3-(2-methylphenoxy)propyl acrylate,4-(2-methylphenoxy)butyl acrylate, 5-(2-methylphenoxy)pentyl acrylate,6-(2-methylphenoxy)hexyl acrylate, 2-(2-methylphenoxy)ethylmethacrylate, 3-(2-methylphenoxy)propyl methacrylate,4-(2-methylphenoxy)butyl methacrylate, 5-(2-methylphenoxy)pentylmethacrylate, 6-(2-methylphenoxy)hexyl methacrylate,2-(2,6-dimethylphenoxy)ethyl acrylate, 3-(2,6-dimethylphenoxy)propylacrylate, 4-(2,6-dimethylphenoxy)butyl acrylate,5-(2,6-dimethylphenoxy)pentyl acrylate, 6-(2,6-dimethylphenoxy)hexylacrylate, 2-(2,6-dimethylphenoxy)ethyl methacrylate,3-(2,6-dimethylphenoxy)propyl methacrylate, 4-(2,6-dimethylphenoxy)butylmethacrylate, 5-(2,6-dimethylphenoxy)pentyl methacrylate,6-(2,6-dimethylphenoxy)hexyl methacrylate, 2-(2-methoxyphenoxy)ethylacrylate, 3-(2-methoxyphenoxy)propyl acrylate, 4-(2-methoxyphenoxy)butylacrylate, 5-(2-methoxyphenoxy)pentyl acrylate, 6-(2-methoxyphenoxy)hexylacrylate, 2-(2-methoxyphenoxy)ethyl methacrylate,3-(2-methoxyphenoxy)propyl methacrylate, 4-(2-methoxyphenoxy)butylmethacrylate, 5-(2-methoxyphenoxy)pentyl methacrylate,6-(2-methoxyphenoxy)hexyl methacrylate, 2-(2,6-dimethoxyphenoxy)ethylacrylate, 3-(2,6-dimethoxyphenoxy)propyl acrylate,4-(2,6-dimethoxyphenoxy)butyl acrylate, 5-(2,6-dimethoxyphenoxy)pentylacrylate, 6-(2,6-dimethoxyphenoxy)hexyl acrylate,2-(2,6-dimethoxyphenoxy)ethyl methacrylate,3-(2,6-dimethoxyphenoxy)propyl methacrylate,4-(2,6-dimethoxyphenoxy)butyl methacrylate,5-(2,6-dimethoxyphenoxy)pentyl methacrylate,6-(2,6-dimethoxyphenoxy)hexyl methacrylate. From the perspectives ofavailability, reactivity in the Friedel-Crafts reaction, and thereactivity of the acryloyl group, 2-phenoxyethyl acrylate is preferable.

When reacting the compound (a2) having a (meth)acryloyl group and aphenoxy group that is represented by the above general formula (2) withthe halogen-terminated polyisobutylene polymer (a1) obtainable bycationic polymerization that is represented by the above general formula(I), it is preferable to use a Lewis acid as a catalyst.

In this case, although the Lewis acid is not especially limited as longas it is a common Lewis acid, Lewis acids such as TiCl₄, Ti(OiPr)₄,TiBr₄, AlCl₃, AlBr₃, Et₂AlCl, Me₂AlCl, EtAlCl₂, MeAlCl₂, Et₂AlBr,Me₂AlBr, EtAlBr₂, MeAlBr₂, Et_(1.5)AlCl_(1.5), Me_(1.5)AlCl_(1.5),Et_(1.5)AlBr_(1.5), Me_(1.5)AlBr_(1.5), BCl₃, BF₃, BF₃(OEt₂), GaCl₃,FeCl₃, FeBr₃, SnCl₄, SnBr₄, SbCl₅, SbBr₅, SbF₅, WCl₆, TaCl₅, VCl₅,ZnCl₂, and ZnBr₂ are preferable because these acids have especially highreactivity and excellent selectivity.

From the perspectives of industrial availability and reactivity, TiCl₄,Ti(OiPr)₄, TiBr₄, AlCl₃, AlBr₃, Et₂AlCl, Me₂AlCl, EtAlCl₂, MeAlCl₂,Et₂AlBr, Me₂AlBr, EtAlBr₂, MeAlBr₂, Et_(1.5)AlCl_(1.5),Me_(1.5)AlCl_(1.5), Et_(1.5)AlBr_(1.5), Me_(1.5)AlBr_(1.5), BCl₃, BF₃,BF₃(OEt₂), GaCl₃, FeCl₃, FeBr₃, SnCl₄, ZnCl₂, and ZnBr₂ Are especiallypreferable.

It is preferable to perform the reaction under conditions in which themolar ratio of the compound (a2) having a (meth)acryloyl group and aphenoxy group to the Lewis acid (a value represented by (number of molesof compound (a2) having a (meth)acryloyl group and a phenoxygroup)/(number of moles of Lewis acid)) is less than 1.0. If this ratiois 1.0 or more, the reactivity of the addition reaction of compound (a2)having a (meth)acryloyl group and a phenoxy group with thehalogen-terminated polyisobutylene polymer (a1) deteriorates, and theintroduction ratio of (meth)acryloyl groups decreases, which are notdesirable. This is thought to be due to the coordination of the compound(a2) having a (meth)acryloyl group and a phenoxy group to the Lewisacid, which causes Lewis acidity to deteriorate.

When reacting the compound (a2) having a (meth)acryloyl group and aphenoxy group with the halogen-terminated polyisobutylene polymer (a1)obtainable by cationic polymerization, these components may be reactedin the absence of a solvent in the case where the mixture including thehalogen-terminated polyisobutylene polymer (a1) and the compound (a2)having a (meth)acryloyl group and a phenoxy group has a low viscosityand can be stirred so that the reaction can be carried out with themixture only.

On the other hand, when using a reaction solvent, for example, a solventarbitrarily selected from among halogenated hydrocarbons, aromatichydrocarbons, and aliphatic hydrocarbons may be used alone or as a mixedsolvent. Regarding the selection of these solvents, from theperspectives of solubility and reactivity under the polymerizationconditions, as a halogenated hydrocarbon, it is preferable to select oneor more components selected from methylene chloride, chloroform,1,1-dichloroethane, 1,2-dichloroethane, n-propyl chloride, and n-butylchloride. For the same reasons, toluene is preferable as an aromatichydrocarbon, and one or more components selected from butane, pentane,hexane, heptane, octane, nonane, decane, cyclohexane, methylcyclohexane, and ethyl cyclohexane are preferable as an aliphatichydrocarbon.

Examples of solvents used in reactions which do not use halogenatedhydrocarbons, which may give negative impact on the environment, includetoluene, ethyl cyclohexane, or a mixed solvent of these. By using suchsolvents, production of the (meth)acryloyl group-terminatedpolyisobutylene polymer represented by general formula (1) can be easilyachieved.

The reaction temperature in the reaction between the halogen-terminatedpolyisobutylene polymer (a1) and the compound (a2) having a(meth)acryloyl group and a phenoxy group represented by the abovegeneral formula (2) is preferably a temperature lower than 0° C. If thereaction is carried out at 0° C. or higher, the introduction ratio ofthe compound (a2) having a (meth)acryloyl group and a phenoxy group maydecrease, which is not desirable. The decrease of the introduction ratiooccurs because the halogen-terminated polyisobutylene undergoes a chaintransfer reaction, so that exo-olefins (isopropenyl groups), inactive inthe Friedel-Crafts reaction, are produced as the terminal functionalgroups of the polyisobutylene.

When reacting the halogen-terminated polyisobutylene polymer (a1) andthe compound (a2) having a (meth)acryloyl group and a phenoxy grouprepresented by the above general formula (2), an isolatedhalogen-terminated polyisobutylene polymer (a1) may be reacted with thecompound (a2) having a (meth)acryloyl group and a phenoxy group, or thereaction may be carried out by adding the compound (a2) having a(meth)acryloyl group and a phenoxy group into the polymerization systemduring the synthesis of the halogen-terminated polyisobutylene polymer(a1).

In the latter case, the timing for adding the compound (a2) having a(meth)acryloyl group and a phenoxy group is preferably at a point whenthe conversion rate of the isobutylene monomer measured by gaschromatography has reached 50% or more, more preferably 80% or more, andeven more preferably 95% or more.

In the present invention, as the compound (a2) having a (meth)acryloylgroup and a phenoxy group represented by the above general formula (2),a commercially-available compound can be used as it is, or a compoundindividually synthesized depending on the intended purpose may be used.

In the latter case, the compound can be simply synthesized by reactingan alcohol compound (a3) represented by the following general formula(3):

wherein R², R³, and R⁴ are the same as described above;

with a compound represented by the following general formula (4):XC(O)C(R⁵)═CH₂  (4)

wherein R⁵ and X are the same as described above.

When reacting the alcohol compound (a3) and the compound represented bygeneral formula (4), in order to accelerate the reaction, a base thatcaptures the produced HX, namely, hydrogen chloride, hydrogen bromide,or hydrogen iodide, may also be added. Examples of the added baseinclude amine compounds such as ammonia, diethylamine, triethylamine,di-n-propylamine, tri-n-propylamine, di-1-propylamine,tri-1-propylamine, di-n-butylamine, tri-n-butylamine, di-1-butylamineand tri-1-butylamine, nitrogen-containing compounds such as pyridine,α-picoline, β-picoline, aniline, methylaniline, dimethylaniline andN,N-dimethylaniline, lithium hydroxide, sodium hydroxide, potassiumhydroxide, rubidium hydroxide, cesium hydroxide, lithium carbonate,sodium carbonate, potassium carbonate, rubidium carbonate, cesiumcarbonate, lithium bicarbonate, sodium bicarbonate, potassiumbicarbonate, rubidium hydrogen carbonate, cesium hydrogen carbonate,lithium hydride, sodium hydride, butyl lithium, lithium diisopropylamideand the like.

When reacting the alcohol compound (a3) and the compound represented bygeneral formula (4), either a solvent system or a solvent-free systemmay be used. If a solvent is used, it is preferable that the solvent bea dehydrated solvent.

When using a solvent, examples of solvents that can be used includehalogenated hydrocarbon solvents such as methylene chloride, chloroform,1,1-dichloroethane, 1,2-dichloroethane, n-propyl chloride and n-butylchloride; aromatic hydrocarbon solvents such as benzene, toluene andxylene; aliphatic hydrocarbon solvents such as pentane, n-hexane,cyclohexane, methyl cyclohexane and ethyl cyclohexane; ethers such asdiethyl ether, dibutyl ether, diisopropyl ether, tetrahydrofuran,dimethoxyethane and dioxane; esters such as ethyl acetate; as well asacetonitrile, pyridine, triethylamine and the like.

The compound (a2) having a (meth)acrylic group and a phenoxy group canbe obtained by reacting the alcohol compound (a3) and the compoundrepresented by general formula (4) for 1 minute to 24 hours at areaction temperature of −70° C. to 200° C., and preferably 0° C. to 100°C.

Another simple method for synthesizing the compound (a2) having a(meth)acryloyl group and a phenoxy group is a reaction of a compound(a4) having a phenoxy group and a halogen group that is represented bygeneral formula (5):

wherein R², R³, R⁴, and X are the same as described above;

with a compound represented by general formula (6):HOC(O)C(R⁵)═CH₂  (6)

wherein R⁵ is the same as described above.

When reacting the compound (a4) having a phenoxy group and a halogengroup and the compound represented by general formula (6), in order toaccelerate the reaction, a base that captures the produced HX, namely,hydrogen chloride, hydrogen bromide, or hydrogen iodide, may also beadded. Examples of the added base include nitrogen-containing compoundssuch as ammonia, diethylamine, triethylamine, di-n-propylamine,tri-n-propylamine, di-1-propylamine, tri-1-propylamine, di-n-butylamine,tri-n-butylamine, di-1-butylamine, tri-1-butylamine, pyridine,α-picoline, β-picoline, aniline, methylaniline, dimethylaniline andN,N-dimethylaniline, lithium hydroxide, sodium hydroxide, potassiumhydroxide, rubidium hydroxide, cesium hydroxide, lithium carbonate,sodium carbonate, potassium carbonate, rubidium carbonate, cesiumcarbonate, lithium bicarbonate, sodium bicarbonate, potassiumbicarbonate, rubidium hydrogen carbonate, cesium hydrogen carbonate,lithium hydride, sodium hydride, potassium hydride, butyl lithium,lithium diisopropylamide and the like.

Further, the compound represented by general formula (6) may be reactedin advance with the above-described base and thus neutralized, and theresultant compound may be reacted with the compound (a4) having aphenoxy group and a halogen group.

When reacting the compound (a4) having a phenoxy group and a halogengroup and the compound represented by general formula (6), either asolvent system or a solvent-free system may be used. If a solvent isused, it is preferable that the solvent be a dehydrated solvent.

When using a solvent, examples of solvents that can be used includehalogenated hydrocarbon solvents such as methylene chloride, chloroform,1,1-dichloroethane, 1,2-dichloroethane, n-propyl chloride and n-butylchloride; aromatic hydrocarbon solvents such as benzene, toluene andxylene; aliphatic hydrocarbon solvents such as pentane, n-hexane,cyclohexane, methyl cyclohexane and ethyl cyclohexane; ethers such asdiethyl ether, dibutyl ether, diisopropyl ether, tetrahydrofuran,dimethoxyethane and dioxane; esters such as ethyl acetate; as well asacetonitrile, pyridine, triethylamine and the like.

the compound (a2) having a (meth)acryloyl group and a phenoxy group canbe obtained by reacting the compound (a4) having a phenoxy group and ahalogen group and the compound represented by general formula (6) for 1minute to 24 hours at a reaction temperature of −70° C. to 200° C., andpreferably 0° C. to 100° C.

Further, the (meth)acryloyl-terminated polyisobutylene polymer (A)represented by general formula (1) according to the present inventioncan also be obtained by a method in which the halogen-terminatedpolyisobutylene polymer (a1) is reacted with a compound (a5) having aphenoxy group, and then reacted with a compound (a6) having a(meth)acryloyl group.

Specifically, the (meth)acryloyl-terminated polyisobutylene polymer (A)can also be synthesized by reacting a polyisobutylene polymer (a7)having a hydroxyl group on an end represented by the following generalformula (7):

wherein A, R¹, R², R³, R⁴, and n are the same as described above;

with a compound represented by the above-described general formula (4):XC(O)C(R⁵)═CH₂  (4)

wherein R⁵ and X are the same as described above. In this case too, the(meth)acryloyl-terminated polyisobutylene polymer (A) can be efficientlysynthesized by using the reaction conditions used in the reactionbetween the above-described alcohol compound (a3) and the compoundrepresented by formula (4).

However, a so-called macromolecular reaction such as the reactionbetween the hydroxyl group-terminated polyisobutylene polymer (a7) andthe compound represented by formula (4) usually has poor reactionefficiency, and also a linear synthesis method generally tends to resultin a lower yield of the target product compared with a convergentsynthesis method. Therefore, this method is recommended only for casesin which there is a particular need.

Further, the (meth)acryloyl-terminated polyisobutylene polymer (A) canalso be synthesized by reacting a polyisobutylene polymer (a8) having ahalogen group on an end represented by the following general formula(8):

wherein A, R¹, R², R³, R⁴, X, and n are the same as described above;

with the above-mentioned compound represented by the general formula(6):HOC(O)C(R⁵)═CH₂  (6)

wherein R⁵ is the same as described above.

In this case too, the (meth)acryloyl-terminated polyisobutylene polymer(A) can be efficiently synthesized by using the reaction conditions usedin the reaction between the above-described compound (a4) having aphenoxy group and a halogen group and the compound represented bygeneral formula (6).

A polymerization inhibitor can be added to the (meth)acryloyl-terminatedpolyisobutylene polymer (A) according to the present invention duringpurification after polymerization or storage if necessary. Examples ofthe polymerization inhibitor may include phenol compounds such ashydroquinone, hydroquinone monomethyl ether, p-tert-butylcatechol,4-methoxy-naphthol, 2,6-di-t-butyl-4-methylphenol,2,2′-methylenebis(4-ethyl-6-t-butylphenol),2,6-di-t-butyl-N,N-dimethylamino-p-cresol, 2,4-dimethyl-6-t-butylphenol,4-t-butylcatechol, 4,4′-thio-bis(3-methyl-6-t-butylphenol) and4,4′-butylidene-bis(3-methyl-6-t-butylphenol); N-oxy radical compoundssuch as 4-hydroxy-2,2,6,6-tetramethylpiperidine-n-oxyl,4-acetamino-2,2,6,6-tetramethylpiperidine-N-oxyl,4-benzoxy-2,2,6,6-tetramethylpiperidine-N-oxyl,4-oxo-2,2,6,6-tetramethylpiperidine-N-oxyl and2,2,6,6-tetramethylpiperidine-N-oxyl; amine compounds such asphenothiazine, N,N′-diphenyl-p-phenylenediamine, phenyl-β-naphthylamine,N,N′-di-β-naphthyl-p-phenylenediamine andN-phenyl-N′-isopropyl-p-phenylenediamine; hydroxylamine compounds suchas 1,4-dihydroxy-2,2,6,6-tetramethylpiperidine and4-dihydroxy-2,2,6,6-tetramethylpiperidine; quinone compounds such asbenzoquinone and 2,5-di-t-butylhydroquinone; ferrous chloride; coppercompounds such as copper dimethyl dithiocarbamate and the like.

These can be used alone or as a mixture of two or more thereof.

Among the above-described polymerization inhibitors, N-oxy radicalcompounds, phenol compounds, amino compounds and hydroxylamine compoundsare preferable. Among these, from the perspective of effectivelysuppressing polymerization, N-oxy radical compounds, N-oxy radicalcompounds and phenol compounds are more preferable.

The above-described polymerization inhibitor can be used with anotherpolymerization inhibitor. If the above-described polymerizationinhibitor is used with another polymerization inhibitor, a betterpolymerization suppression effect can be obtained based on a synergisticeffect from the use of the two inhibitors.

From the perspective of sufficiently exhibiting a polymerizationsuppression effect, the amount of the polymerization inhibitor to beused is 1 to 5,000 ppm by mass based on the (meth)acryloyl-terminatedpolyisobutylene polymer, and desirably is 50 to 3,000 ppm by mass.

The active energy ray-curable composition according to the presentinvention contains an (meth)acryloyl-terminated polyisobutylene polymer(A) represented by the following general formula (1):

wherein R¹ represents a monovalent or polyvalent aromatic hydrocarbongroup, or a monovalent or a polyvalent aliphatic hydrocarbon group; Arepresents a polyisobutylene polymer; R² represents a divalent saturatedhydrocarbon group having 2 to 6 carbon atoms, which contains no heteroatoms; R³ and R⁴ each represent hydrogen, a monovalent hydrocarbon grouphaving 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbonatoms; R⁵ represents hydrogen or a methyl group; and n denotes a naturalnumber, and

an active energy ray polymerization initiator (B).

It is preferable to use as the active energy ray polymerizationinitiator (B) a photo-radical initiator or a photo-anionic initiator.The initiator to be used can be used alone or as a mixture of two ormore thereof. When using a mixture, the amount of each initiator to beused is preferably within the respective ranges described below.

Although the active energy ray polymerization initiator (B) used in thepresent invention is not especially limited, photo-radical initiatorsand photo-anionic initiators are preferable, and photo-radicalinitiators are especially preferable. Examples thereof includeacetophenone, propiophenone, benzophenone, xanthol, fluorene,benzaldehyde, anthraquinone, triphenylamine, carbazole,3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone,2,2-diethoxyacetophenone, 4-methoxyacetophen, 3-bromoacetophenone,4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone,4-methylbenzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone,4-chloro-4′-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone,3-chloro-8-nonylxanthone, benzoyl, benzoin methyl ether, benzoin butylether, bis(4-dimethylaminophenyl)ketone,bis(4-diethylaminophenyl)ketone, 2,4,6-trimethylbenzophenone,3,3′-dimethyl-4-methoxybenzophenone, 2-benzoyl benzoic acid, methyl2-benzoylbenzoate, dibenzosuberone, benzyl methoxy ketal,2-chlorothioxanthone, 2,2-dimethoxy-1,2-diphenylethan-1-one,1-hydroxy-cyclohexyl-phenyl-ketone,2-hydroxy-2-methyl-1-phenyl-propan-1-one,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide,bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide,2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and the like. Amongthese, a compound having a hydroxyl group and a phenyl ketone structure,a compound having a benzophenone structure, and a compound having anacyl phosphine oxide structure are preferable. Specifically,3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone,4,4′-dimethoxybenzophenone, 4-chloro-4′-benzylbenzophenone,1-hydroxy-cyclohexyl-phenyl-ketone,2-hydroxy-2-methyl-1-phenyl-propan-1-one,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide,bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide are preferable.Especially 2,2-dimethoxy-1,2-diphenylethan-1-one,1-hydroxy-cyclohexyl-phenyl-ketone,2-hydroxy-2-methyl-1-phenyl-propan-1-one,bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide are preferable. Theseinitiators can be used alone or in combination with another compound.Specific examples thereof include a combination with an amine, such asdiethanol/methylamine, dimethylethanolamine, and triethanolamine, aswell as a combination in addition to this with an iodonium salt such asdiphenyl iodonium chloride, or a combination with a pigment such asMethylene blue and an amine.

When using the above-described active energy ray polymerizationinitiator (B), a polymerization inhibitor such as hydroquinone,hydroquinone monomethyl ether, benzoquinone, and p-tert-butylcatecholmay be added if necessary.

Further, a near-infrared ray-absorbing cationic dye may be used as anear-infrared active energy ray polymerization initiator. As thenear-infrared ray-absorbing cationic dye, it is preferable to use anear-infrared ray absorbing cationic dye-borate anionic complex or thelike disclosed in, for example, JP 3-111402 A and JP 5-194619 A, whichis excited by light energy in the region of 650 to 1,500 nm, and morepreferable to use it with a boron-based sensitizer.

Although the amount of the active energy ray polymerization initiator(B) to be added is not especially limited, 0.001 to 20 parts by weightper 100 parts by weight of the polyisobutylene polymer (A) ispreferable, and 0.05 to 10 parts by weight is more preferable. If theamount of the active energy ray polymerization initiator to be added is0.001 parts by weight or less, sufficient curing properties may not beobtained. On the other hand, if the amount to be added is 20 parts byweight or more, the active energy rays do not reach the deeper portions,so that an uncured layer may form on the composition surface, or thethick film curability may deteriorate, or the heat resistance of thecured product may deteriorate.

Although the method for curing the active energy ray-curable compositionaccording to the present invention is not especially limited, examplesmay include irradiating light or an electron beam with a high pressuremercury lamp, a low pressure mercury lamp, an electron beam irradiationdevice, a halogen lamp, a light emitting diode, a semiconductor laserand the like, depending on the nature of the active energy raypolymerization initiator.

To adjust the various physical properties of the active energyray-curable composition according to the present invention or the curedproduct thereof, various additives may be added to the composition orcured product if necessary. Examples of such additives include anadhesion promoter, a plasticizer, a filler, fine hollow particles, aphysical property modifier, a silanol-containing compound, a lightstabilizer, a mold release agent, a flame retardant, a radicalpolymerization inhibitor, a metal deactivator, an antiozonant, a UVabsorber, a lubricant, a pigment, a blowing agent and the like. Thesevarious additives can be used alone or in combination of two or morethereof.

Specific examples of such additives are described in variousspecifications and the like, such as WO 2007-069600, JP 4-69659 B, JP7-108928 B, JP 63-254149 A, and JP 64-22904 A. Depending on the intendedpurpose, the active energy ray-curable composition according to thepresent invention may also be used with a polymerizable monomer and/oroligomer or various additives. As the polymerizable monomer and/oroligomer, a monomer and/or oligomer having a radical-polymerizablegroup, or a monomer and/or oligomer having an anion-polymerizable groupis preferable.

Examples of the radical-polymerizable group include an acrylicfunctional group such as a (meth)acrylic group, a styrene group, anacrylonitrile group, a vinyl ester group, an N-vinylpyrrolidone group,an acrylamide group, a conjugated diene group, a vinyl ketone group, avinyl chloride group and the like. Among these, a group having a(meth)acrylic group is preferable. Examples of the anion-polymerizablegroup include a (meth)acrylic group, a styrene group, an acrylonitrilegroup, an N-vinylpyrrolidone group, an acrylamide group, a conjugateddiene group, a vinyl ketone group and the like. Among these, an acrylicfunctional group is preferable.

Specific examples of the above-described monomers include a(meth)acrylate monomer, a cyclic acrylate, N-vinylpyrrolidone, a styrenemonomer, acrylonitrile, N-vinylpyrrolidone, an acrylamide monomer, aconjugated diene monomer, a vinyl ketone monomer and the like.

Examples of the (meth)acrylate monomer include (meth)acrylic acid,methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate,isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl(meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate,isoamyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl(meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate,2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl(meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl(meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl(meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate,hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, stearyl(meth)acrylate, isostearyl (meth)acrylate, behenyl (meth)acrylate,phenyl (meth)acrylate, toluoyl (meth)acrylate, tolyl (meth)acrylate,4-tert-butylcyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate,dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate,dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate,tetrahydrofurfuryl (meth)acrylate, 3,3,5-trimethylcyclohexyl(meth)acrylate, adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl(meth)acrylate, 1-methyladamantyl (meth)acrylate, 1-ethyladamantyl(meth)acrylate, 3,5-dihydroxy-1-adamantyl (meth)acrylate, benzyl(meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-butoxyethyl(meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxybutyl(meth)acrylate, phenoxyethyl (meth)acrylate, ethylcarbitol(meth)acrylate, methoxy triethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate, 2-ethylhexyl diethylene glycol (meth)acrylate,methoxy-dipropylene glycol (meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl(meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl(meth)acrylate, 1,4-cyclohexanedimethanol (meth)acrylate, glycerin(meth)acrylate, polyethylene glycol (meth)acrylate (Blemmer PE-90,PE-200, PE-350, PE-350G, AE-90, AE-200, AE-400 etc., manufactured by NOFCorporation), polypropylene glycol (meth)acrylate (Blemmer PP-500,PP-800, PP-1000, AP-150, AP-400, AP-550 etc., manufactured by NOFCorporation), polyethylene glycol-polypropylene glycol (meth)acrylate(Blemmer 50PEP-300, 70PEP-350B etc., manufactured by NOF Corporation),polyethylene glycol-polypropylene glycol (meth)acrylate, polyethyleneglycol-polytetramethylene glycol (meth)acrylate, polypropyleneglycol-polytetramethylene glycol (meth)acrylate, polyethyleneglycol-polybutylene glycol (meth)acrylate, glycidyl (meth)acrylate,4-hydroxybutyl-glycidyl ether (meth)acrylate, dimethylaminoethyl(meth)acrylate, diethylaminoethyl (meth)acrylate, a dimethylaminoethyl(meth)acrylate quaternary product (Light Ester DQ-100, DQ-75, etc.,manufactured by Kyoeisha Chemical Co., Ltd.),2-methyl-2-ethyl-1,3-dioxolane 4-(meth)acrylate,1,4-dioxaspiro[4,5]dec-2-ylmethyl 2-(meth)acrylate (CHDOL-10,manufactured by Osaka Organic Chemical Industry Ltd.),3-ethyl-3-oxetanyl (meth)acrylate (OXE-10, manufactured by Osaka OrganicChemical Industry Ltd.), γ-butyrolactone (meth)acrylate,2-phenylthioethyl (meth)acrylate, 2-hydroxy-3-(2-propenyloxy)propyl(meth)acrylate, a phthalic anhydride-2-hydroxypropyl (meth)acrylateadduct (Viscoat #2100, manufactured by Osaka Organic Chemical IndustryLtd.), 2-(meth)acryloyloxyethyl phthalic acid (Light Ester HPA-MPLmanufactured by Kyoeisha Chemical Co., Ltd., CB-1 manufactured byShin-Nakamura Chemical Co., Ltd., etc.),mono{1-methyl-2-[(1-oxo-2-propenyl)oxy]ethyl}ester1,2-cyclohexyldicarboxylate (Viscoat #2150 manufactured by Osaka OrganicChemical Industry Ltd.), (meth)acryloyloxy-ethylhexahydrophthalate(Light Ester HO-HH, HOA-HH etc., manufactured by Kyoeisha Chemical Co.,Ltd.), (meth)acryloyloxyethylsuccinate (Light Ester HO-MS and HOA-MSmanufactured by Kyoeisha Chemical Co., Ltd., SA and A-SA manufactured byShin-Nakamura Chemical Co., Ltd., etc.),2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalic acid (Light EsterHO-MPP etc., manufactured by Kyoeisha Chemical Co., Ltd.),2-(meth)acryloyloxyethyl-hydroxyethyl phthalate (HOA-MPE etc.,manufactured by Kyoeisha Chemical Co., Ltd.),2-(meth)acryloyloxyethyl-phosphate (Light Ester P-1M, P-2M, etc.,manufactured by Kyoeisha Chemical Co., Ltd.), ethoxylated-o-phenylphenol(meth)acrylate, methoxy polyethylene glycol (meth)acrylate, (Light EsterMC, 130MA, 041MA, MTG, MTG-A, and 130A manufactured by Kyoeisha ChemicalCo., Ltd., M-90G, AM-90G, M-230G, and AM130G manufactured byShin-Nakamura Chemical Co., Ltd., Fancryl FA-400M manufactured byHitachi Chemical Co., Ltd., Blemmer PME-100, PME-200, PME-400, PME-550,PME-1000, PME-4000, and AME-400 manufactured by NOF Corporation etc.),phenoxy polyethylene glycol (meth)acrylate (Light Acrylate P-200Amanufactured by Kyoeisha Chemical Co., Ltd., AMP-20GY manufactured byShin-Nakamura Chemical Co., Ltd., Blemmer PAE-50, PAE-100, AAE-50, andAAE-300 manufactured by NOF Corporation, Aronix M-101 and M-102manufactured by Toagosei Co., Ltd., etc.), paracumylphenoxyethyl(meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate (LightAcrylate NP-4EA and NP-8EA manufactured by Kyoeisha Chemical Co., Ltd.,Fancryl FA-314A and FA-318A manufactured by Hitachi Chemical Co., Ltd.,Blemmer ANE-1300 manufactured by NOF Corporation, M-111, M113, and M-117manufactured by Toagosei Co., Ltd., etc.), octoxypolyethyleneglycol-polypropylene glycol (meth)acrylate, lauroxypolyethylene glycol(meth)acrylate, stearoxypolyethylene glycol (meth)acrylate,phenoxy-polyethylene glycol-polypropylene glycol (meth)acrylate,nonylphenoxy-polyethylene glycol-polypropylene glycol (meth)acrylate,3-chloro-2-hydroxypropyl (meth)acrylate, 2-(2-vinyloxyethoxy)ethyl(meth)acrylate, allyloxy polyethylene glycol-polypropylene glycol(meth)acrylate, undecyleneoxy (meth)acrylate, undecylenoxy polyethyleneglycol (meth)acrylate, ω-carboxy-polycaprolactone (meth)acrylate (M-5300etc., manufactured by Toagosei Co., Ltd.), dimer acrylate (M-5600manufactured by Toagosei Co., Ltd., β-CEA manufactured by Daicel-CytecCo., Ltd., etc.), N-ethylmaleimide (meth)acrylate,pentamethylpiperidinyl (meth)acrylate, tetramethylpiperidinyl(meth)acrylate, γ-(methacryloyloxypropyl)trimethoxysilane,γ-(methacryloyloxypropyl)triethoxysilane,γ-(methacryloyloxypropyl)methyldimethoxysilane, 2-isocyanate ethyl(meth)acrylate, 2-(0-[1′-methylpropylideneamino]carboxyamino)ethyl(meth)acrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl(meth)acrylate, zinc (meth)acrylate, potassium (meth)acrylate, sodium(meth)acrylate, magnesium (meth)acrylate, calcium (meth)acrylate, barium(meth)acrylate, strontium (meth)acrylate, nickel (meth)acrylate, copper(meth)acrylate, aluminum (meth)acrylate, lithium (meth)acrylate,neodymium (meth)acrylate, trifluoromethyl methyl (meth)acrylate,2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl(meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate,perfluoroethylmethyl (meth)acrylate, 2-perfluoroethylethyl(meth)acrylate, perfluoroethylperfluorobutylmethyl (meth)acrylate,2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, perfluoroethyl(meth)acrylate, perfluoromethyl (meth)acrylate, diperfluoromethylmethyl(meth)acrylate, 2,2-diperfluoromethylethyl (meth)acrylate,perfluoromethylperfluoroethylmethyl (meth)acrylate,2-perfluoromethyl-2-perfluoroethylethyl (meth)acrylate,2-perfluorohexylmethyl (meth)acrylate, 2-perfluorohexylethyl(meth)acrylate, 2-perfluorodecylmethyl (meth)acrylate,2-perfluorodecylethyl (meth)acrylate, 2-perfluorohexadecylmethyl(meth)acrylate, 2-perfluorohexadecylethyl (meth)acrylate and the like.Here, (meth)acrylate represents acrylate and/or methacrylate, and(meth)acryloyl represents acryloyl and/or methacryloyl.

Further examples include aromatic vinyl monomers such as styrene, vinylketone, α-methylstyrene, p-methylstyrene, chlorostyrene, styrenesulfonic acid, salts thereof and the like; fluorine-containing vinylmonomers such as perfluoroethylene, perfluoropropylene, and vinylidenefluoride; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyl triethoxysilane; maleic anhydride, maleicacid, and monoalkyl and dialkyl esters of maleic acid; fumaric acid andmonoalkyl and dialkyl esters of fumaric acid; maleimide monomers such asmaleimide, methylmaleimide, ethylmaleimide, propylmaleimide,butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide,stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide;acrylonitrile monomers such as acrylonitrile and methacrylonitrile;amide group-containing vinyl monomers such as acrylamide,methacrylamide, and N,N-dimethyl acrylamide; vinyl esters such as vinylacetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinylbenzoate, and vinyl cinnamate; alkenes such as ethylene and propylene;conjugated dienes such as butadiene and isoprene; vinyl chloride,vinylidene chloride, vinyl iodide, vinyl bromide, vinylidene bromide,allyl chloride, allyl alcohol, vinyl ether, methyl vinyl ketone and thelike. These can be used alone or by copolymerizing a plurality thereof.

Examples of the polyfunctional monomer include di(meth)acrylates of asaturated hydrocarbon diol such as 1,9-nonanediol di(meth)acrylate,1,10-decanediol di(meth)acrylate, 1,6-hexane di(meth)acrylate, neopentylglycol di(meth)acrylate, 1,4-butane di(meth)acrylate, 1,3-butanedi(meth)acrylate, and 1,2-ethylene di(meth)acrylate; bifunctional(meth)acrylate compounds such as neopentyl glycol polyethoxydi(meth)acrylate, neopentyl glycol polypropoxy di(meth)acrylate,polyethylene glycol di(meth)acrylate, polypropylene glycoldi(meth)acrylate, polyethylene glycol-polypropylene glycoldi(meth)acrylate, polypropylene glycol-polytetramethylene glycoldi(meth)acrylate, glycerin di(meth)acrylate, polytetramethylene glycoldi(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate,cyclohexanedimethanol di(meth)acrylate, bisphenol A diethoxydi(meth)acrylate, EO-modified bisphenol A di(meth)acrylate, PO-modifiedbisphenol A di(meth)acrylate, PO-EO-modified bisphenol Adi(meth)acrylate, tetrabromobisphenol A diethoxy di(meth)acrylate,4,4-dimercaptodiphenylsulfide di(meth)acrylate, bisphenol F polyethoxydi(meth)acrylate, bisphenol A polyethoxy di(meth)acrylate,2-(2-(meth)acryloyloxy-1,1-dimethyl)-5-ethyl-5-acryloyloxymethyl-1,3-dioxane,2-[5-ethyl-5-[(acryloyloxy)methyl]-1,3-dioxan-2-yl]-2,2-dimethylethyl,and 1,1-(bis-(meth)acryloyloxymethyl)ethylisocyanate; trifunctional(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate,trimethylolpropanepolyethoxy tri(meth)acrylate,trimethylolpropanepolypropoxy tri(meth)acrylate, tetramethylolmethanetri(meth)acrylate, isocyanuric acid tri(meth)acrylate, ethoxylatedisocyanuric acid tri(meth)acrylate, pentaerythritol tri(meth)acrylate,and glycerin tri(meth)acrylate; and polyfunctional (meth)acrylatecompounds such as dipentaerythritol hexa(meth)acrylate,tris(hydroxyethyl)isocyanuratepolyhexanolide tri(meth)acrylate,pentaerythritol tetra(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate.

Examples of the oligomer include epoxy acrylate resins such as abisphenol A-type epoxy acrylate resin, a phenol novolak type epoxyacrylate resin, a cresol novolak type epoxy acrylate resin, and a COOHgroup-modified epoxy acrylate resin; a urethane acrylate resin obtainedby reacting a urethane resin obtained from a polyol (polytetramethyleneglycol, a polyester diol of ethylene glycol and adipic acid, anε-caprolactone-modified polyester diol, polypropylene glycol,polyethylene glycol, polycarbonate diol, hydroxyl group-terminatedhydrogenated polyisoprene, hydroxyl group-terminated polybutadiene,hydroxyl group-terminated hydrogenated polybutadiene, and hydroxylgroup-terminated polyisobutylene etc.) and an organic isocyanate(tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, xylylene diisocyanate etc.)with a hydroxyl group-containing (meth)acrylate {hydroxyethyl(meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl(meth)acrylate, pentaerythritol triacrylate etc.}; a resin into which a(meth)acrylic group has been introduced via an ester bond to theabove-described polyol; and a so-called macromonomer, such as apolyester acrylate resin, a poly (meth)acrylacrylate resin (apoly(meth)acrylate resin having a polymerizable reaction group), amethyl methacrylate resin having a (meth)acryloyl group at one end, astyrene resin, a styrene/acrylonitrile resin, polybutyl acrylate,polyisobutyl methacrylate, a methyl methacrylate/hydroxyethylmethacrylate copolymer resin, a 2-ethylhexyl methacrylate/hydroxyethylmethacrylate copolymer resin, and a silicone resin.

Here, (meth)acrylic acid means acrylic acid and/or methacrylic acid,(meth)acrylate means acrylate and/or methacrylate, and (meth)acryloylmeans acryloyl and/or methacryloyl.

These monomers and oligomers are selected based on the initiator to beused and the curing conditions.

Further, these monomers and oligomers can be used alone or incombination of two or more thereof.

In addition, the number average molecular weight of the monomer and/oroligomer having an acrylic functional group is preferably 2,000 or less,and more preferably 1,000 or less as compatibility is good.

Although the content of the polymerizable monomer and/or oligomer is notespecially limited, 0.1 to 200 parts by weight per 100 parts by weightof the (meth)acryloyl-terminated polyisobutylene polymer (A) ispreferable, and 1 to 50 parts by weight is more preferable. If thecontent is less than 0.1 parts by weight, the effect of improvingphysical properties may not be obtained. On the other hand, if thecontent is 200 parts by weight or more, the degree of curability may betoo high or heat resistance may deteriorate.

A photocurable substance other than the (meth)acryloyl-terminatedpolyisobutylene polymer (A) according to the present invention may beadded, if necessary, to the active energy ray-curable compositionaccording to the present invention. A photocurable substance is asubstance in which the molecular structure undergoes a chemical changein a short period of time due to the action of light, which causeschange in properties such as curing. By adding this photocurablesubstance, the tackiness of the cured product surface (also referred toas residual tack) can be reduced when the curable composition is cured.Although this photocurable substance is a substance that can be cured byan irradiation of light, a representative photocurable substance is asubstance that can be cured by leaving at room temperature for 1 dayindoors in a place that receives sunlight (near a window), for example.Many compounds are known as such a compound, such as an organic monomer,an oligomer, a resin, or a composition including these. Although thetype of this compound is not especially limited, examples thereof mayinclude unsaturated acrylic compounds, polyvinyl cinnamates, azideresins or the like.

An unsaturated acrylic compound is a monomer, oligomer, or a mixturethereof having an unsaturated group represented by the following generalformula (9):CH₂═CHR⁶CO(O)—  (9)

wherein R⁶ represents an alkyl group having 1 to 10 carbon atoms, anaryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to10 carbon atoms.

Specific examples of the unsaturated acrylic compound include a(meth)acrylate of a low molecular weight alcohol such as ethyleneglycol, glycerin, trimethylolpropane, pentaerythritol, and neopentylalcohol; a (meth)acrylate of a polyester polyol having a main chain of apolyester and a hydroxyl group on an end, a (meth)acrylate of a polyolhaving a main chain of a vinyl-type or a (meth)acrylate-type polymer anda hydroxyl group in the main chain and the like; an epoxy acrylateoligomer obtained by reacting a bisphenol A-type or a novolak type epoxyresin with a (meth)acrylic acid; and a urethane acrylate oligomer havinga urethane bond and a (meth)acrylic group in the molecular chainobtained by reacting a polyol, a polyisocyanate and a hydroxylgroup-containing (meth)acrylate and the like.

A polyvinyl cinnamate is a photosensitive resin having a cinnamoyl groupas a photosensitive group. Examples include, in addition to a compoundobtained by esterifying a polyvinyl alcohol with cinnamic acid, manypolyvinyl cinnamate derivatives.

Azide resins are known as a photosensitive resin having an azide groupas a photosensitive group. In addition to a rubber photosensitivesolution obtained by adding an azide compound as a photosensitive agent,examples are described in detail in “Photosensitive Resins” (publishedon Mar. 17, 1972, by Insatsu Gakkai Shuppanbu Ltd., page 93 onwards,page 106 onwards, and page 117 onwards). These may be used alone ormixed, and a sensitizing agent may be added if necessary.

Among the above-described photocurable substances, unsaturated acryliccompounds are preferable because it is easy to handle them.

It is preferable to add 0.01 to 20 parts by weight of the photocurablesubstance per 100 parts by weight of the (meth)acryloyl-terminatedpolyisobutylene polymer (A). If the amount added is less than 0.01 partsby weight, the effect is small. On the other hand, if the amount addedis more than 20 parts by weight, there can be an adverse impact on thephysical properties. Further, if a sensitizing agent, such as a ketone,a nitro compound, or a promoter, such as an amine, is added, the effectscan be increased.

An air-oxidation curable substance may also be added, if necessary, tothe active energy ray-curable composition according to the presentinvention. An air-oxidation curable substance is a compound that has anunsaturated group capable of being crosslinked and cured by oxygen inthe air. By adding this air-oxidation curable substance, the tackinessof the cured product surface (also referred to as residual tack) can bereduced when the curable composition is cured. This air-oxidationcurable substance in the present invention is a substance that can becured when brought into contact with air. More specifically, it has acharacter of being cured by reacting with oxygen in the air. Arepresentative air-oxidation curable substance can be cured by leavingfor 1 day indoors in air, for example.

Specific examples of the air-oxidation curable substance include dryingoils such as tung oil and linseed oil; various alkyd resins obtained bymodifying these drying oils; acrylic polymers, epoxy resins, andsilicone resins modified by a drying oil; a polymer or a copolymer of1,2-polybutadiene, 1,4-polybutadiene, or a C5 to C8 diene, as well asvarious modified products of such polymers or copolymers (maleatedmodified products, boiled oil-modified products etc.) and the like.Among these, tung oil and liquid products of a diene polymer (liquiddiene polymers) or a modified product thereof are especially preferable.

Specific examples of the above-described liquid diene polymer include aliquid polymer obtained by polymerizing or copolymerizing a dienecompound such as butadiene, chloroprene, isoprene, 1,3-pentadiene, apolymer, such as NBR or SBR, which can be obtained by copolymerizingsuch a diene compound as the main component and a monomer such asacrylonitrile or styrene that can be copolymerized with the dienecompound, as well as various modified products thereof (maleatedmodified products, boiled oil-modified products etc.) and the like.These can be used alone or in combination of two or more thereof. Amongthese diene compounds, polybutadiene, polyisoprene, andpoly(1,3-pentadiene) are preferable.

The air-oxidation curable substance can be used alone or in combinationof two or more thereof. Further, if the air-oxidation curable substanceis simultaneously used with a catalyst or a metal dryer that promotes anoxidative curing reaction, the effects can be increased. Examples ofsuch catalysts and metal dryers include metal salts, such as cobaltnaphthenate, lead naphthenate, zirconium naphthenate, cobalt octoate,and zirconium octoate, and amine compounds.

It is preferable to add 0.01 to 20 parts by weight of the air-oxidationcurable substance per 100 parts by weight of the polyisobutylene polymer(A). If the amount added is less than 0.01 parts by weight, the effectis small, while if the amount added is more than 20 parts by weight,there can be an adverse impact on the physical properties.

From the perspective of improving gas barrier properties, thecomposition according to the present invention may also contain anethylene-vinyl alcohol copolymer. It is preferable that the ethylenecontent in the ethylene-vinyl alcohol copolymer be 20 to 70 mol %. Ifthe ethylene content is less than 20 mol %, not only are moisturebarrier properties and flexibility poor, but flex resistance and heatmoldability can also be poor. Further, if the ethylene content is morethan 70 mol %, gas barrier properties may be insufficient. The contentof the ethylene-vinyl alcohol copolymer is preferably 1 to 400 parts byweight per 100 parts by weight of the polyisobutylene polymer (A), andmore preferably 10 to 400 parts by weight. If the content of theethylene-vinyl alcohol copolymer is more than 400 parts by weight,flexibility can be lost and bending fatigue properties in the long termmay deteriorate.

The composition according to the present invention may also contain atackifier. Examples of the tackifier include natural rosin, a terpenephenolic resin having a hydroxyl value (OH value) of 50 mgKOH/g or less,a synthetic coumaroneindene resin, a petroleum resin, an alkylphenolresin and the like. The content of the tackifier is preferably 1 to 80parts by weight per 100 parts by weight of the polyisobutylene blockcopolymer. Depending on the intended purpose, a filler, a softener, anda processing aid may further be added to the composition according tothe present invention. Examples of a filler include carbon black, wetsilica, dry silica, calcium carbonate, kaolin, talc, clay and the like.Examples of a softener include paraffinic oils, naphthenic oils,aromatic oils, rapeseed oil, dioctyl phthalate, dioctyl adipate and thelike. Examples of a processing aid include higher fatty acids, fattyacid esters, fatty acid metal salts, fatty acid amides, paraffin wax,fatty alcohols, fluorine- or silicone-based resins, and high molecularweight polyethylene.

The composition according to the present invention may also contain anantioxidant if necessary.

Examples of the antioxidant include hindered phenol antioxidants,hindered amine antioxidants, phosphorus antioxidants, sulfurantioxidants, and amine antioxidants.

The hindered phenol antioxidant is not especially limited, andconventionally known hindered phenol antioxidants may be widely used.From the perspectives of compatibility with the curable composition andexcellent heat resistance of the obtained cured product, preferablehindered phenol antioxidants include ADK STAB AO-50, ADK STAB AO-80,IRGANOX-1010, IRGANOX-1076, IRGANOX-1141, IRGANOX-1520, and SumilizerGA-80.

The hindered amine antioxidant is not especially limited, andconventionally known hindered amine antioxidants may be widely used. Thehindered amine antioxidants are compounds having at least one hinderedpiperidine group in one molecule.

From the perspectives of storage stability of the curable compositionand excellent weatherability of the obtained cured product, preferablehindered amine antioxidants include ADK STAB LA-63, ADK STAB LA-63P,TINUVIN 152, TINUVIN 123, Sanol LS765, Hostavin N24, and Hostavin N30.

The phosphorus antioxidant is not especially limited, and an arbitrarycompound can be used. Since phosphoric acid and phosphates that containan active hydrogen affect the storage stability of the composition andthe heat resistance of the cured product, alkyl phosphites, arylphosphites, alkyl aryl phosphite compounds and the like that do notinclude phosphoric acid or a phosphate in the molecule are preferable.

With regard to the phosphorus antioxidant, it is preferable that atleast two substituents on the phosphorus atom are aryloxy groups fromthe perspectives of stability against hydrolysis and excellent heatresistance. Specifically preferable examples of phosphorus antioxidantsinclude ADK STAB 1178, ADK STAB 329K, ADK STAB 135A, ADK STAB C, ADKSTAB TPP, ADK STAB 2112, ADK STAB HP-10, JPM-313, JPP-100, CHELEX-M, andIRGAFOS 38.

The amine antioxidant used in the present invention is not especiallylimited, and conventionally known amine antioxidants may be widely used.Specific examples of amine-ketone compounds include a2,2,4-trimethyl-1,2-dihydroquinoline polymer,6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, and the reaction productof a diphenylamine and acetone. Examples given in terms of specifictrade names include, but are not limited to, Nocrac 224, Nocrac AW,Nocrac AW-N, Nocrac B, and Nocrac B-N (all manufactured by Ouchi ShinkoChemical Industrial Co., Ltd.), Antage RD, Antage RD-G, and Antage AW(all manufactured by Kawaguchi Chemical Industry Co., Ltd.), NONFLEX RD,NONFLEX QS, NONFLEX AW, NONFLEX BA, NONFLEX BA-P, and NONFLEX BAR (allmanufactured by Seiko Chemical Co., Ltd.), Vulkanox HS/LG, VulkanoxHS/powder (both manufactured by Bayer AG), Korestab TMQ (manufactured byS&S Japan Co., Ltd.), and Aminox (manufactured by Shiraishi CalciumKaisha, Ltd.).

Examples of aromatic amine compounds include naphthylamine-basedantioxidants, diphenylamine-based antioxidants, andp-phenylenediamine-based antioxidants. From the perspective of excellentheat resistance, 4,4′-bis(α,α-dimethylbenzyl)diphenylamine,N,N′-di-2-naphthyl-p-phenylenediamine, andN-phenyl-N′-(3-methacryloyloxy-2-hydroxypropyl)-p-phenylenediamine aremore preferable as the aromatic amine antioxidant.

The sulfur antioxidant is not especially limited, and conventionallyknown sulfur antioxidants may be widely used. However, sincethiol-containing compounds affect the curability, a sulfur antioxidantthat has a thioether structure in the molecule is preferable. Specificexamples include 4,4′-thiobis(3-methyl-6-tert-butylphenol),dilauryl-thiodipropionate, bis{2-methyl-4-[3-n-alkyl(C₁₂ orC₁₄)thiopropionyloxy]-5-tert-butyl phenyl}sulfide,pentaerythrityl-tetrakis(3-laurylthiopropionate),ditridecyl-3,3′-thiodipropionate, distearyl-thiodipropionate,2,2-thio-diethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],4,6-bis[(octylthio)methyl]o-cresol,2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine,dimyristyl-3,3′-thiodipropionate, dibutyl methylene-bis-thioglycolateand the like.

It is preferable to add 0.1 to 20 parts by weight of the anti-agingagent per 100 parts by weight of the (meth)acryloyl-terminatedpolyisobutylene polymer (A). If the amount is less than 0.1 parts byweight, the heat resistance of the cured product may be insufficient. Onthe other hand, if the amount is more than 20 parts by weight, there canbe an adverse impact on the physical properties and curing properties.These antioxidants can be used alone or in combination of two or morethereof. If combining two or more, it is preferable to combine a primaryantioxidant such as a hindered phenol antioxidant or a hindered amineantioxidant, and a secondary antioxidant such as a phosphorusantioxidant or a sulfur antioxidant.

Although the method for preparing the active energy ray-curablecomposition according to the present invention is not especiallylimited, the active energy ray-curable composition may be prepared as aone-pack type by blending all of the components to be added or preparedas a two-pack type by separately blending the components to be added, inconsideration of the storage stability of the composition and the like,which are to be mixed before use.

In the case of a one-pack type, it is not necessary to carry out mixingand kneading when applying, and measurement mistakes (mistakes in themixing ratio) are also eliminated during such work. Consequently,mistakes such as curing defects can be prevented.

In the case of a two-pack type, the components to be blended can bearbitrarily divided into two packs which are to be mixed before use.When dividing into a pack A and a pack B, various combinations can beemployed in consideration of the mixing ratio, storage stability, mixingmethod, potlife and the like of the curable composition.

Further, if necessary, a three-pack curable composition can be employedby preparing a third component in addition to the pack A and the pack B.Moreover, the components to be blended can be divided even more asnecessary.

The method for mixing the composition according to the present inventionis not especially limited. For example, the composition can be producedby blending the above-described components, shading the blend from lightif necessary, and kneading the blend using a hand mixer, a static mixer,a planetary mixer, a disperser, a roll, a kneader, a single-screwextruder, a twin-screw extruder, a Banbury mixer, a Brabender mixer, ahigh-shear mixer and the like. Regarding the temperature of kneading, acommon method may be employed, such as kneading at an ordinarytemperature or under heating, or using a small amount of a suitablesolvent to dissolve the components and mixing.

The cured product according to the present invention that is obtained bycuring with active energy rays can be formed as a rubber-like curedproduct or as a gel-like cured product. The composition of the curedproduct is characterized by having a very low halogen atom content. Thecontent of halogen atoms coming from the polyisobutylene polymer can be500 ppm or less, and more preferably can be 100 ppm or less.

The cured product according to the present invention has excellentcuring properties of the cured product surface. Namely, it wasdiscovered that the active energy ray-curable composition according tothe present invention has the excellent characteristic that thecrosslinking reaction at the composition surface caused by active energyrays is less susceptible to inhibition caused by oxygen and the like.Therefore, the cured product according to the present invention has theexcellent characteristic that a resin-like uncured layer is not formedon the surface of the cured product after irradiation of active energyrays.

Although applications of the active energy ray-curable composition andcured product according to the present invention are not limited, theycan be used in various applications, such as for a sealing material, asealant, a coating material, a potting material, a fixed gasket, aformed-in-place gasket, an adhesive, a pressure-sensitive adhesive, afiller, a molding, a foam, a film, a casting material, an ink, ananti-vibration material, a damping material, a soundproofing material, aseismic isolation material and the like.

In electrical and electronic applications, for example, the activeenergy ray-curable composition and cured product according to thepresent invention can be used for an LED material, various batteryperipheral materials, a sensor, a semiconductor peripheral material, acircuit board peripheral material, a display peripheral material forliquid crystals and the like, an optical communication/optical circuitperipheral material, an optical recording peripheral material, amagnetic recording material and the like.

For an LED material, the active energy ray-curable composition and curedproduct according to the present invention can be used as a moldingmaterial, a sealant, a sealing film, a die-bonding material, a coatingmaterial, a sealing material, an adhesive, a pressure-sensitiveadhesive, a lens material and the like for an LED element, as well as asealing material, an adhesive, a pressure-sensitive adhesive, a coatingmaterial and the like for an LED bulb, an LED indicator, an LED displayboard, an LED display device and the like.

For a battery peripheral material, the active energy ray-curablecomposition and cured product according to the present invention can beused as a sealing material, a rear face sealant, a molding material forvarious elements, an adhesive, a pressure-sensitive adhesive, a sealant,a sealing film, a coating material, a potting material, a filler, aseparator, a catalyst fixing film, a protective film, an electrodebinding agent, a sealing material for refrigerant oil, a hose materialand the like for a lithium-ion battery, a sodium-sulfur battery, asodium molten-salt battery, a nickel-metal hydride battery, a nickelcadmium battery, a redox flow battery, a lithium sulfur battery, an airbattery, an electrolytic capacitor, an electric double layer capacitor,a lithium ion capacitor, a fuel cell, a solar cell, a dye-sensitizedsolar cell and the like.

For a sensor, the active energy ray-curable composition and curedproduct according to the present invention can be used as a sealant, asealing film, a lens material, an adhesive, a pressure-sensitiveadhesive, a coating agent, a film and the like for various kinds ofsensor, such as a sensor for power, load, pressure, rotation, vibration,flow rate, solar radiation, light, smell, time, temperature, humidity,wind speed, distance, position, inertia, slope, velocity, acceleration,angular velocity, hardness, strain, sound, magnetism, current, voltage,power, electron, radiation, infrared ray, X-ray, UV-ray, fluid volume,weight, gas volume, ion content, metal content, color and the like.

For a circuit board peripheral material, the active energy ray-curablecomposition and cured product according to the present invention can beused as a sealing material, a coating material, a potting material, amolding material for each of the below-described elements, an underfillmaterial, a die-bonding material, a die bonding film, an adhesive, apressure-sensitive adhesive, a sealant, a sealing film and the like fora rigid or a flexible wiring board or MEMS (micro-electro-mechanicalsystem) on which various elements are mounted, such as an IC, an LSI, asemiconductor chip, a transistor, a diode, a thyristor, a capacitor, aresistor, a coil and the like.

For a display peripheral material, the active energy ray-curablecomposition and cured product according to the present invention can beused as a molding material for various elements, various filters, a filmsuch as a protective film, an antireflection film, a viewing anglecompensation film, a polarizer protective film and an opticalcompensation film, a sealing material, an adhesive, a pressure-sensitiveadhesive, a sealant, a sealing film, a coating material of a substrateor a material, a potting agent, a filler, a visibility improver, a lensmaterial, a light guide plate, a prism sheet, a polarizing plate, aretardation plate, and a liquid crystal dam material for a liquidcrystal display, a plasma display, a LED display device, an organic EL(electroluminescence) display, a field emission display, electronicpaper, a flexible display, a 3D hologram, an organic thin filmtransistor display, and a head-mounted display and the like.

For an optical communication/optical circuit peripheral material, theactive energy ray-curable composition and cured product according to thepresent invention can be used as a molding material for variouselements, a sealing material, an adhesive, a pressure-sensitiveadhesive, a sealant, a sealing film, a coating material, a pottingagent, a filler, a protective film, a lens material, a light guideplate, a prism sheet, a polarizing plate, a ferrule and the like for anorganic photorefractive element, an optical fiber, an optical switch, alens, an optical waveguide, a light emitting element, a photodiode, anoptical amplifier, an optoelectronic integrated circuit, an opticalconnector, an optical coupler, an optical processing element, aphotoelectric converter, a laser element and the like.

For an optical recording material, the active energy ray-curablecomposition and cured product according to the present invention can beused as a protective film, a sealing material, an adhesive, apressure-sensitive adhesive, a sealant, a sealing film, a coatingmaterial, an anti-vibration material, and a damping material for a VD(video disc), a CD, a CD-ROM, a CD-R, a CD-RW, a DVD, a DVD-ROM, aDVD-R, a DVD-RW, a BD, a BD-ROM, a BD-R, a BD-RE, an MO, an MD, a PD(phase change disc), a hologram, a disc substrate material for anoptical card, a pickup lens and the like.

For a magnetic recording material, the active energy ray-curablecomposition and cured product according to the present invention can beused as a vibration-proofing material, a damping material, a sealingmaterial, an adhesive, a pressure-sensitive adhesive, a sealant, acoating material, a cover gasket, and a card material for a hard disk, amagnetic tape, and a magnetic card such as a credit card.

In addition, the active energy ray-curable composition and cured productaccording to the present invention can also be used as a touch paneldirt-resistant film, a lubricating film, an IC chip molding material, aPeltier element molding material, an electrolytic capacitor sealingbody, a cable joint potting material, a potting material for an IGBT (avehicle propulsion control device), a semiconductor wafer processingdicing tape, a die-bonding agent, a die-bonding film, underfill, ananisotropic conductive adhesive, an anisotropic conductive film, aconductive adhesive, a conductive paste, a thermally conductiveadhesive, a thermally conductive paste, a temporary fixing film, afixing film, a sealing film and the like.

In automotive applications, as a body part, the active energyray-curable composition and cured product according to the presentinvention may be used as a sealing material for maintainingairtightness, an anti-vibration material for glass, a car body sectionvibration-proofing material, and especially as a window seal gasket anda door glass gasket. As a chassis part, the active energy ray-curablecomposition and cured product according to the present invention can beused as engine or suspension rubber for vibration proofing and soundproofing, and especially as an engine-mounted rubber and a sealingmaterial for a vibration proofing mount. As an engine part, the activeenergy ray-curable composition and cured product according to thepresent invention can be used for a hose for cooling, fuel supply,exhaust control and the like, a gasket for an engine cover or an oilpan, an engine oil sealing material and the like. Further, as a tirepart, the active energy ray-curable composition and cured productaccording to the present invention can be used as a bead portion, asidewall portion, a shoulder portion, and a tread portion, or as asealing material for an inner liner resin or an air-pressure sensor orpuncture sensor. In addition, the active energy ray-curable compositionand cured product according to the present invention can be used as asealing material, a sealant, a gasket, a coating material, a moldingmember, an adhesive, and a pressure-sensitive adhesive for variouselectronic components and control components. Still further, the activeenergy ray-curable composition and cured product according to thepresent invention can be used as a covering material for a wire harnessmade from copper or aluminum, or as a sealing material for a connectorpart. Additionally, the active energy ray-curable composition and curedproduct according to the present invention can also be used as a sealingmaterial, an adhesive, a pressure-sensitive adhesive, molded part suchas a gasket, an O-ring, packing and a belt, and the like, for a lamp, abattery, a windshield washer fluid unit, an air conditioning unit, acoolant unit, a brake oil unit, an electrical part, various interior andexterior parts, an oil filter and the like, as well as a pottingmaterial for an igniter HIC or an automotive hybrid IC.

In industrial applications, the active energy ray-curable compositionand cured product according to the present invention can be used forresist applications, such as permanent resist applications, solderresist applications, dry-film resist applications, and electrodepositionresist applications.

For information electrical devices, the active energy ray-curablecomposition and cured product according to the present invention can beused as a sealing material, a sealant, an adhesive, a pressure-sensitiveadhesive, packing, an O-ring, a belt, a vibration-proofing material, adamping material, a sound-proofing material and the like for a mobilephone, a media player, a tablet terminal, a smartphone, a portable gamemachine, a computer, a printer, a scanner, a projector, an inkjet tankand the like.

In the field of consumer electronics, the active energy ray-curablecomposition and cured product according to the present invention can beused as a sealing material, an adhesive, a pressure-sensitive adhesive,packing, an O-ring, a belt, a vibration-proofing material, a dampingmaterial, a sound-proofing material and the like for various electricalproducts, such as a television, various recorders, such as a Blu-rayrecorder and an HDD recorder, a projector, a game console, a digitalcamera, a home video machine, an antenna, a speaker, an electronicdictionary, an IC recorder, a FAX, a copying machine, a telephonemachine, an intercom, a rice cooker, a microwave oven, an oven range, arefrigerator, a dishwasher, a tableware dryer, an IH cooking heater, ahotplate, a vacuum cleaner, a washing machine, a charger, a sewingmachine, an iron, a dryer, an electric bicycle, an air purifier, a waterpurifier, an electric toothbrush, lighting fixtures, an air conditioner,an outdoor air conditioner, a dehumidifier, a humidifier and the like.

For leisure applications, the active energy ray-curable composition andcured product according to the present invention can be used for a pieceof swimming equipment, such as a swimming cap, a diving mask, and an earplug, a gel cushioning member in sports shoes, baseball gloves and thelike, an adhesive or a shock absorber in a golf ball, a club, a racketand the like.

For a molding, the active energy ray-curable composition and curedproduct according to the present invention can be used as packing, anO-ring, a belt, a tube, a hose, a valve, a sheet and the like.

Further, the active energy ray-curable composition and cured productaccording to the present invention can also be used for a reactive hotmelt agent for a wiring connector, and for various kinds of adhesive,such as a reactive hot melt adhesive, an OCA (optically transparentadhesive), an elastic adhesive, a contact adhesive, an anaerobicadhesive, a UV-ray curable adhesive, an electron beam curable adhesiveand the like.

The active energy ray-curable composition and cured product according tothe present invention can also be used as an improver for butyl-basedpressure-sensitive adhesive, or as various kinds of pressure-sensitiveadhesive, such as pressure-sensitive adhesive for masking tape, pipeanti-corrosion tape, architectural waterproofing tape, self-fusingelectrical tape, a removable pressure-sensitive adhesive, a fusing tapefor electrical wire, and the like.

The active energy ray-curable composition and cured product according tothe present invention can also be used in various coating applications,such as for a wiring or cable covering material or repair materialthereof, an insulation sealing material for a wire connection portion, atube inner liner for a gas pipe or a water pipe, a coating material foran inorganic filler and an organic filler, a release material for amolding in an epoxy mold and the like.

The active energy ray-curable composition and cured product according tothe present invention can also be used for various sheets, such as aheat conduction sheet, a heat dissipation sheet, an electromagnetic waveabsorption sheet, a conductive sheet, a waterproof sheet, an automotiveprotective sheet, and a panel shock absorbing sheet.

In addition, the active energy ray-curable composition and cured productaccording to the present invention can be used for a shock absorbinggel, a shock absorbing material in beds, shoes and the like, anintermediate layer film for laminated glass, a paint such as an elasticpaint or an aqueous emulsion, a prepreg, various rollers for OAequipment and conveyance equipment, a cap liner, an ink repellent, ink,sealing materials for various refrigerant, a sealing material or gasketfor industrial and food cans, a foam gasket, and a primary and secondaryseal of double-glazed glass.

In medical applications, the active energy ray-curable composition andcured product according to the present invention can be used for apressure-sensitive adhesive for a transdermal drug or patch, apharmaceutical or medical sealing material, a medical pressure-sensitiveadhesive, a medical rubber stopper, an impression material, a dentalfilling material, a syringe gasket, a decompressed blood vessel rubberstopper, an O-ring or a flat gasket for artificial dialysis equipment,drug or medical equipment packaging materials, a cap, a cap liner, avacuum blood collection tube cap, a catheter sealing material oradhesive, a sealing material or adhesive for an implanted medical deviceand the like.

For damping material and vibration-proofing material applications, theactive energy ray-curable composition and cured product according to thepresent invention can also be used in electrical and electronic deviceapplications, such as for a damping material in a stepping motor, amagnetic disk, a hard disk, a dishwasher, a dryer, a washing machine, afan heater, a sewing machine, a vending machine, a speaker frame, a BSantenna, and a VTR cover; architectural applications, such as in a roof,flooring, a shutter, a curtain rail, a floor, a plumbing duct, a deckplate, a curtain wall, stairs, a doors, a seismic isolator, a structuraldamping material, a viscoelastic damper, and a seismic resistingmaterial; marine applications, such as a damping material in an engineroom or a measurement room; automotive applications, such as for adamping material in an engine (oil pan, front cover, rocker cover), acar body (dashboard, floor, doors, roof, panels, wheel house), atransmission, a parking brake cover, and a damping material for seatback; camera and office equipment applications, such as a dampingmaterial for a TV camera, a copying machine, a computer, a printer, acash register, and a cabinet; industrial applications, such as for adamping material in a shooter, an elevator, an escalator, a conveyor, atractor, a bulldozer, a power generator, a compressor, a container, ahopper, a soundproof box, and lawn mower motor cover; railwayapplications, such as a damping material in a railway carriage roof, aside plate, a door, an underfloor, various auxiliary covers, and abridge; a damping material for precision anti-vibration equipment forsemiconductor applications and the like; and for a damping material forsoundproofing of low-frequency sounds and high-frequency sounds near theaudible threshold region.

EXAMPLES

Although the present invention will now be described in more detail withreference to the examples, the present invention is not limited to theseexamples. Further, the various measurement methods and evaluationmethods will be described before the examples.

(Molecular Weight Measurement)

In the below examples, “number average molecular weight”, “weightaverage molecular weight” and “molecular weight distribution (ratio ofthe number average molecular weight and weight average molecularweight)” were calculated by a standard polystyrene conversion methodusing size permeation chromatography (SEC). As the SEC system, the LCModule 1 manufactured by Waters Corporation was used. As the GPC column(stationary phase), a column filled with a polystyrene crosslinked gel(Shodex GPC K-804, manufactured by Showa Denko K.K.) was used. As themobile phase, chloroform was used.

(Calculation of Functionalization Rate Fn)

The molecular weight of the polymer was calculated from the above GPCmeasurement to determine the number average molecular weight Mn. Next,¹H-NMR measurement was carried out, and using the above-mentioned numberaverage molecular weight Mn, the surface area of the peaks attributableto the two methyl groups in the polyisobutylene skeleton near 1.3 ppmwas calculated as follows.(Integral value of the peaks near 1.3 ppm)=((Number average molecularweight Mn)/56.11)×6H

At this stage, the average value of the peaks in the same ¹H-NMR chartderived from a (meth)acryloyl group appearing near 5.8 to 5.9 ppm, 6.1to 6.2 ppm, and 6.4 ppm was calculated. This averaged integral value wasused as the number of functionalization Fn.

(Gel Fraction)

About W₁ g of the cured product obtained in each of the followingexamples and comparative examples was measured out, and dipped inn-hexane (in an amount of about 200 times that of W₁). The resultantmixture was left to stand at 70° C. for 24 hours. Then, the mixture wascooled to room temperature. The precipitate was then recovered byfiltration, and dried at 80° C. under reduced pressure for 24 hours. Theweight W₂ of the obtained solid was measured, and the gel fraction wasdetermined based on the following calculation equation.Gel fraction (%)=W ₂ /W ₁×100  Calculation equation:(Residual Chlorine Concentration)

The amount of chlorine in the obtained copolymer was determined underthe following conditions. As the measurement sample, a sample obtainedby dissolving the obtained polymer in toluene and then reprecipitatingin methanol to remove the chlorine species not bound to the copolymermolecules was used.

Measurement apparatus: TOX-10S, manufactured by Mitsubishi ChemicalCorporation

Combustion temperature: 900° C.

Detection method: Oxidation and coulometric titration method

Measurement method: Same sample measured three times, and the averagevalue thereof was taken as the measurement value.

(Gas Permeability)

<Oxygen Permeability>

The oxygen permeability was measured by a differential-pressure methodunder a condition of 1 atm, 23° C. and 0% RH in conformity with JISK7126.

<Water Vapor Permeability>

The water vapor permeability was measured at 40° C., 90% RH inconformity with JIS 20208.

Further, the following was used as the active energy ray polymerizationinitiator.

(Active Energy Ray Polymerization Initiator)

Twenty parts by weight of DAROCURE 1173(2-hydroxy-2-methyl-1-phenyl-propan-1-one, manufactured by Ciba JapanK.K.) and 10 parts by weight of IRGACURE 819(bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, manufactured by CibaJapan K.K.) were measured out, and thoroughly mixed for 5 minutes with aspatula to prepare an active energy ray polymerization initiator mixture[1].

Example 1 Production of Acryloyl-Terminated Polyisobutylene Polymer(Component P-1)

A 5 L separable flask was purged with nitrogen, and then the flask wascharged with 280 mL of n-hexane (which had been dried with a molecularsieve) and 2,500 mL of butyl chloride (which had been dried with amolecular sieve), and while stirring under a nitrogen atmosphere, cooledto −70° C. Next, 1,008 mL (10.7 mol) of isobutylene, 27.4 g (0.119 mol)of p-dicumyl chloride, and 1.33 g (0.014 mol) of α-picoline were added.The resultant reaction mixture was cooled to −70° C., then charged with5.2 mL (0.047 mol) of titanium tetrachloride to start polymerization.After the polymerization started, the residual isobutylene concentrationwas measured by gas chromatography. When the residual amount ofisobutylene fell below 0.5%, about 200 g of methanol was added. Thesolvent and the like was removed by evaporation from the reactionsolution, and the resultant product was then dissolved in 2 L ofn-hexane and washed three times with 1 L of pure water. The solvent wasremoved by evaporation under reduced pressure, and the obtained polymerwas dried under vacuum for 24 hours at 80° C. to obtain achlorine-terminated polyisobutylene polymer A-1. The molecular weight ofthe obtained polymer A-1 based on polystyrene was measured by sizeexclusion chromatography (SEC). Mw was 5,800, Mn was 5,200, and Mw/Mnwas 1.12.

Next, 100 g of the obtained polyisobutylene polymer A-1, 540 ml of butylchloride, 60 ml of n-hexane, and 15.2 g of 2-phenoxyethyl acrylate(manufactured by Tokyo Chemical Industry Co., Ltd.) were charged into a1 L separable flask, and the resultant mixture was cooled to −70° C.while stirring. After the cooling to −70° C. or less had been completed,22 ml of titanium tetrachloride was added. Then, after a continuousstirring for 6 hours at −70° C., 200 ml of methanol was added to stopthe reaction. After fractionation of the supernatant from the reactionsolution, and the removal of the solvent and the like by evaporation,the product was dissolved in 650 ml of n-hexane, washed three times with500 ml of pure water, and reprecipitated from methanol. The solvent wasthen removed by evaporation under reduced pressure, and the obtainedpolymer was dried under vacuum for 24 hours at 80° C. to obtain thetarget acryloyl-terminated polyisobutylene polymer P-1. The molecularweight of the obtained polymer P-1 based on polystyrene was measured bysize exclusion chromatography (SEC). Mw was 6,000, Mn was 5,400, andMw/Mn was 1.11. Further, the Fn of the acryloyl groups introduced ontothe end of the obtained acryloyl-terminated polyisobutylene P-1 was1.93.

Example 2 Production of Acryloyl-Terminated Polyisobutylene Polymer(Component P-2)

A 1 L separable flask was purged with nitrogen, and then the flask wascharged with 40 mL of n-hexane (which had been dried with a molecularsieve) and 400 mL of butyl chloride (which had been dried with amolecular sieve), and while stirring under a nitrogen atmosphere, cooledto −70° C. Next, 168 mL (1.78 mol) of isobutylene, 4.57 g (0.0198 mol)of p-dicumyl chloride, and 0.222 g (0.00233 mol) of α-picoline wereadded. The resultant reaction mixture was cooled to −70° C., thencharged with 1.0 mL (0.0091 mol) of titanium tetrachloride to startpolymerization. After the polymerization started, the residualisobutylene concentration was measured by gas chromatography. When theresidual amount of isobutylene fell below 0.5%, 15.2 g of 2-phenoxyethylacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 22 mlof titanium tetrachloride were added. Then, after a continuous stirringfor 3 hours at −70° C., 200 ml of methanol was added to stop thereaction. After fractionation of the supernatant from the reactionsolution, and the removal of the solvent and the like by evaporation,the product was dissolved in 550 ml of n-hexane, washed three times with500 ml of pure water, and reprecipitated from methanol. The solvent wasthen removed by evaporation under reduced pressure, and the obtainedpolymer was dried under vacuum for 24 hours at 80° C. to obtain thetarget acryloyl-terminated polyisobutylene polymer P-2. The molecularweight of the obtained polymer P-2 based on polystyrene was measured bysize exclusion chromatography (SEC). Mw was 6,300, Mn was 5,700, andMw/Mn was 1.11. Further, the Fn of the acryloyl groups introduced ontothe end of the obtained acryloyl-terminated polyisobutylene P-2 was1.90.

Example 3 Production of Acryloyl-Terminated Polyisobutylene Polymer(Component P-3)

To 200 ml of N,N-dimethylformamide were added 40.0 g of 6-phenoxyhexylbromide (manufactured by Tokyo Chemical Industry Co., Ltd., 0.0778 mol),85.7 g of potassium acrylate (manufactured by Nippon Shokubai Co., Ltd.,0.778 mol), and 0.5 g of potassium iodide (manufactured by Wako PureChemical Industries, Ltd.), and stirring was continued for 24 hours at150° C. Next, about 75% of the charged solvent was removed byevaporation under reduced pressure. Then, the resultant product wasdissolved in 200 ml of toluene, washed once with 100 ml of saturatedaqueous potassium carbonate, three times with 100 ml of pure water, oncewith 100 ml of saturated brine, and then dried over anhydrous magnesiumsulfate. Next, the solid matter was removed by filtration, and thesolvent in the filtrate was removed by evaporation under reducedpressure to obtain 6-phenoxyhexyl acrylate.

A 300 ml separable flask was purged with nitrogen, and then the flaskwas charged with 15 mL of n-hexane (which had been dried with amolecular sieve) and 130 mL of butyl chloride (which had been dried witha molecular sieve), and while stirring under a nitrogen atmosphere,cooled to −70° C. Next, 50 mL (0.535 mol) of isobutylene, 1.37 g(0.00595 mol) of p-dicumyl chloride, and 0.0665 g (0.0007 mol) ofα-picoline were added. The resultant reaction mixture was cooled to −70°C., then charged with 0.26 mL (0.0023 mol) of titanium tetrachloride tostart polymerization. After the polymerization started, the residualisobutylene concentration was measured by gas chromatography. When theresidual amount of isobutylene fell below 0.5%, 14.8 g (0.0595 mol) of6-phenoxyhexyl acrylate (manufactured by Tokyo Chemical Industry Co.,Ltd.) and 13.1 mL (0.119 mol) of titanium tetrachloride were added, andstirring was continued for 4 hours at −70° C. Then, about 70 g ofmethanol was added. After removal of the solvent and the like from thereaction solution by evaporation, the product was dissolved in 300 ml ofn-hexane, and washed three times with 300 ml of pure water. The solventwas then removed by evaporation under reduced pressure, and the obtainedpolymer was dried under vacuum for 24 hours at 80° C. to obtain theacryloyl-terminated polyisobutylene polymer P-3. The molecular weight ofthe obtained polymer P-3 based on polystyrene was measured by sizeexclusion chromatography (SEC). Mw was 6,000, Mn was 5,500, and Mw/Mnwas 1.09.

Further, the Fn of the acryloyl groups introduced onto the end of theobtained acryloyl-terminated polyisobutylene P-3 was 1.92.

Example 4 Production of Acryloyl-Terminated Polyisobutylene Polymer(Component P-4)

A 1 L separable flask was purged with nitrogen, and then the flask wascharged with 40 mL of n-hexane (which had been dried with a molecularsieve) and 400 mL of butyl chloride (which had been dried with amolecular sieve), and while stirring under a nitrogen atmosphere, cooledto −70° C. Next, 168 mL (1.78 mol) of isobutylene, 4.57 g (0.0198 mol)of p-dicumyl chloride, and 0.222 g (0.00233 mol) of α-picoline wereadded. The resultant reaction mixture was cooled to −70° C., thencharged with 1.0 mL (0.0091 mol) of titanium tetrachloride to startpolymerization. After the polymerization started, the residualisobutylene concentration was measured by gas chromatography. When theresidual amount of isobutylene fell below 0.5%, 16.3 g (0.0791 mol) of2-phenoxyethyl methacrylate (trade name: Light Ester PO, manufactured byKyoeisha Chemical Co., Ltd.) and 22 ml of titanium tetrachloride wereadded. Then, after a continuous stirring for 3 hours at −70° C., 200 mlof methanol was added to stop the reaction. After fractionation of thesupernatant from the reaction solution, and the removal of the solventand the like by evaporation, the product was dissolved in 550 ml ofn-hexane, washed three times with 500 ml of pure water, andreprecipitated from methanol. The solvent was then removed byevaporation under reduced pressure, and the obtained polymer was driedunder vacuum for 24 hours at 80° C. to obtain the targetacryloyl-terminated polyisobutylene polymer P-4. The molecular weight ofthe obtained polymer P-4 based on polystyrene was measured by sizeexclusion chromatography (SEC). Mw was 6,300, Mn was 5,700, and Mw/Mnwas 1.11. Further, the Fn of the methacryloyl groups introduced onto theend of the obtained acryloyl-terminated polyisobutylene P-4 was 1.91.

Comparative Example 1 Production of Acryloyl-Terminated PolyisobutylenePolymer (Component Q-1)

A 5 L separable flask was purged with nitrogen, and then the flask wascharged with 280 mL of n-hexane (which had been dried with a molecularsieve) and 2,500 mL of butyl chloride (which had been dried with amolecular sieve), and while stirring under a nitrogen atmosphere, cooledto −70° C. Next, 1,008 mL (10.7 mol) of isobutylene, 27.4 g (0.119 mol)of p-dicumyl chloride, and 1.33 g (0.014 mol) of α-picoline were added.The resultant reaction mixture was cooled to −70° C., then charged with5.2 mL (0.047 mol) of titanium tetrachloride to start polymerization.After the polymerization started, the residual isobutylene concentrationwas measured by gas chromatography. When the residual amount ofisobutylene fell below 0.5%, about 200 g of methanol was added. Thesolvent and the like was removed by evaporation from the reactionsolution, and the resultant product was then dissolved in 2 L ofn-hexane and washed three times with 1 L of pure water. The solvent wasremoved by evaporation under reduced pressure, and the obtained polymerwas dried under vacuum for 24 hours at 80° C. to obtain achlorine-terminated polyisobutylene polymer A-1. The molecular weight ofthe obtained polymer A-1 based on polystyrene was measured by sizeexclusion chromatography (SEC). Mw was 5,800, Mn was 5,200, and Mw/Mnwas 1.12.

Next, 100 g of the obtained polyisobutylene polymer A-1, 540 ml of butylchloride, 60 ml of n-hexane, and 18.7 g (0.0791 mol) of phenoxypolyethylene glycol acrylate (trade name: Light Acrylate P-200A,manufactured by Kyoeisha Chemical Co., Ltd.) were charged into a 1 Lseparable flask, and the resultant mixture was cooled to −70° C. whilestirring. After the cooling to −70° C. or less had been completed, 22 mlof titanium tetrachloride was added. Then, after a continuous stirringfor 6 hours at −70° C., 200 ml of methanol was added to stop thereaction. After fractionation of the supernatant from the reactionsolution, and the removal of the solvent and the like by evaporation,the product was dissolved in 650 ml of n-hexane, washed three times with500 ml of pure water, and reprecipitated from methanol. The solvent wasthen removed by evaporation under reduced pressure, and the obtainedpolymer was dried under vacuum for 24 hours at 80° C. to obtain thetarget acryloyl-terminated polyisobutylene polymer Q-1. The molecularweight of the obtained polymer Q-1 based on polystyrene was measured bysize exclusion chromatography (SEC). Mw was 6,000, Mn was 5,300, andMw/Mn was 1.13. Further, the Fn of the acryloyl groups introduced ontothe end of the obtained acryloyl-terminated polyisobutylene Q-1 was0.06.

Comparative Example 2 Production of Acryloyl-Terminated PolyisobutylenePolymer (Component Q-2)

A 5 L separable flask was purged with nitrogen, and then the flask wascharged with 280 mL of n-hexane (which had been dried with a molecularsieve) and 2,500 mL of butyl chloride (which had been dried with amolecular sieve), and while stirring under a nitrogen atmosphere, cooledto −70° C. Next, 1,008 mL (10.7 mol) of isobutylene, 27.4 g (0.119 mol)of p-dicumyl chloride, and 1.33 g (0.014 mol) of α-picoline were added.The resultant reaction mixture was cooled to −70° C., then charged with5.2 mL (0.047 mol) of titanium tetrachloride to start polymerization.After the polymerization started, the residual isobutylene concentrationwas measured by gas chromatography. When the residual amount ofisobutylene fell below 0.5%, about 200 g of methanol was added. Thesolvent and the like was removed by evaporation from the reactionsolution, and the resultant product was then dissolved in 2 L ofn-hexane and washed three times with 1 L of pure water. The solvent wasremoved by evaporation under reduced pressure, and the obtained polymerwas dried under vacuum for 24 hours at 80° C. to obtain achlorine-terminated polyisobutylene polymer A-1. The molecular weight ofthe obtained polymer A-1 based on polystyrene was measured by sizeexclusion chromatography (SEC). Mw was 5,800, Mn was 5,200, and Mw/Mnwas 1.12.

Next, 100 g of the obtained polyisobutylene polymer A-1, 540 ml of butylchloride, 60 ml of n-hexane, and 15.2 g (0.0791 mol) of 2-phenoxyethylacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) werecharged into a 1 L separable flask, and 22 ml of titanium tetrachloridewas added to the resultant mixture while stirring at room temperature.Then, after continuing the stirring for 6 hours at −70° C., 200 ml ofmethanol was added to stop the reaction. After fractionation of thesupernatant from the reaction solution, and the removal of the solventand the like by evaporation, the product was dissolved in 650 ml ofn-hexane, washed three times with 500 ml of pure water, andreprecipitated from methanol. The solvent was then removed byevaporation under reduced pressure, and the obtained polymer was driedunder vacuum for 24 hours at 80° C. to obtain the targetacryloyl-terminated polyisobutylene polymer Q-2. The molecular weight ofthe obtained polymer Q-2 based on polystyrene was measured by sizeexclusion chromatography (SEC). Mw was 6,000, Mn was 5,500, and Mw/Mnwas 1.09. Further, the Fn of the acryloyl groups introduced onto the endof the obtained acryloyl-terminated polyisobutylene Q-2 was 0.12.

Comparative Example 3 Production of Acryloyl-Terminated PolyisobutylenePolymer (Component Q-3)

A 1 L separable flask was purged with nitrogen, and then the flask wascharged with 40 mL of n-hexane (which had been dried with a molecularsieve) and 400 mL of butyl chloride (which had been dried with amolecular sieve), and while stirring under a nitrogen atmosphere, cooledto −70° C. Next, 168 mL (1.78 mol) of isobutylene, 4.57 g (0.0198 mol)of p-dicumyl chloride, and 0.222 g (0.00233 mol) of α-picoline wereadded. The resultant reaction mixture was cooled to −70° C., thencharged with 1.0 mL (0.0091 mol) of titanium tetrachloride to startpolymerization. After the polymerization started, the residualisobutylene concentration was measured by gas chromatography. When theresidual amount of isobutylene fell below 0.5%, 15.2 g of 2-phenoxyethylacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added.Then, after a continuous stirring for 3 hours at −70° C., 200 ml ofmethanol was added to stop the reaction. After fractionation of thesupernatant from the reaction solution, and the removal of the solventand the like by evaporation, the product was dissolved in 550 ml ofn-hexane, washed three times with 500 ml of pure water, andreprecipitated from methanol. The solvent was then removed byevaporation under reduced pressure, and the obtained polymer was driedunder vacuum for 24 hours at 80° C. to obtain the targetacryloyl-terminated polyisobutylene polymer Q-3. The molecular weight ofthe obtained polymer Q-3 based on polystyrene was measured by sizeexclusion chromatography (SEC). Mw was 6,100, Mn was 5,300, and Mw/Mnwas 1.15. Further, the Fn of the acryloyl groups introduced onto the endof the obtained acryloyl-terminated polyisobutylene Q-3 was 0.14.

Example 5

A curable composition was obtained by measuring out 100 parts by weightof the acryloyl-terminated polyisobutylene P-1 obtained in Example 1 and2 parts by weight of an active energy ray polymerization initiatormixture [1], and stirring for 5 minutes by hand using a spatula. Then,this curable composition was poured into a metal frame (100 mm×100mm×0.5 mm) made of SUS304, and passed through a UV irradiation device(Model: LH6, manufactured by Fusion UV Systems Japan KK, irradiationconditions: illuminance 1,166 mW/cm² and light amount 2,600 mJ/cm²) toobtain a sheet-like cured product. The gel fraction, residual chlorineconcentration, and gas permeability of the obtained cured product wereevaluated. The results are shown in Table 1.

Example 6

A curable composition was obtained by measuring out 100 parts by weightof the acryloyl-terminated polyisobutylene P-1 obtained in Example 1 and2 parts by weight of an active energy ray polymerization initiatormixture [1], and stirring for 5 minutes by hand using a spatula. Then,this curable composition was poured into a metal frame (100 mm×100mm×0.5 mm) made of SUS304, and passed through a UV irradiation device(Model: LH6, manufactured by Fusion UV Systems Japan KK, irradiationconditions: illuminance 500 mW/cm² and light amount 1,000 mJ/cm²) toobtain a sheet-like cured product. The gel fraction, residual chlorineconcentration, and gas permeability of the obtained cured product wereevaluated. The results are shown in Table 1.

Example 7

A curable composition was obtained by measuring out 100 parts by weightof the acryloyl-terminated polyisobutylene P-1 obtained in Example 1 and1 part by weight of an active energy ray polymerization initiatormixture [1], and stirring for 5 minutes by hand using a spatula. Then,this curable composition was poured into a metal frame (100 mm×100mm×0.5 mm) made of SUS304, and passed through a UV irradiation device(Model: LH6, manufactured by Fusion UV Systems Japan KK, irradiationconditions: illuminance 1,166 mW/cm² and light amount 2,600 mJ/cm²) toobtain a sheet-like cured product. The gel fraction, residual chlorineconcentration, and gas permeability of the obtained cured product wereevaluated. The results are shown in Table 1.

Example 8

A curable composition was obtained by measuring out 100 parts by weightof the acryloyl-terminated polyisobutylene P-3 obtained in Example 3 and2 parts by weight of an active energy ray polymerization initiatormixture [1], and stirring for 5 minutes by hand using a spatula. Then,this curable composition was poured into a metal frame (100 mm×100mm×0.5 mm) made of SUS304, and passed through a UV irradiation device(Model: LH6, manufactured by Fusion UV Systems Japan KK, irradiationconditions: illuminance 1,166 mW/cm² and light amount 2,600 mJ/cm²) toobtain a sheet-like cured product. The gel fraction, residual chlorineconcentration, and gas permeability of the obtained cured product wereevaluated. The results are shown in Table 1.

Comparative Example 4 Production of Acryloyl-Terminated PolyisobutylenePolymer (Component Q-4)

A 5 L separable flask was provided with a three-way cock, athermocouple, and a stirring device equipped with a vacuum seal, andpurged with nitrogen. The flask was then charged with 592 ml of tolueneand 73.6 ml of ethylcyclohexane that had been dehydrated with amolecular sieve 3A, and then further charged with1,4-bis(1-chloro-1-methylethyl)benzene (5.56 g, 24.0 mmol),2-methylpyridine (264 mg, 2.83 mmol), and cooled to −70° C. Aftercooling, an isobutylene monomer (120 ml, 1.44 mol) was introduced, andthen titanium tetrachloride (2.52 ml, 23.0 mmol) was further added atthis temperature to start polymerization. During this process thetemperature rose by about 15° C. The polymerization completed in about60 minutes (as the polymerization completed, heat released from thereaction system was no longer observed). After the polymerizationfinished, octadienyl acetate (32.4 g, 193 mmol) and titaniumtetrachloride (39.8 ml, 386 mmol) were added. After reacting for 5hours, the reaction mixture was brought into 1.5 L of deionized waterheated to 80° C., and the resultant mixture was stirred for 20 minutes.After leaving the mixture to stand, the aqueous layer was removed, and 1L of 2N aqueous sodium hydroxide and 10.0 g of tetrabutylammoniumbromide were added. The resultant mixture was then stirred for 12 hoursat 100° C. After the reaction was completed, the aqueous alkalinesolution was removed. After washing three times with 1 L of deionizedwater, the organic layer was isolated. Then 10 L of acetone was added tothe organic layer to reprecipitate the polymer, and low molecular weightcompounds were then removed. The precipitate was further washed twicewith 1 L of acetone, and further dissolved in 500 ml of hexane. Thesolution was transferred to a 1 L eggplant-shaped flask, and the solventwas removed by evaporation under reduced pressure (1 Torr or less at theend) by heating with an oil bath (180° C.) to obtain the targetpolyisobutylene q-4 terminated with a hydroxyl group (number averagemolecular weight 5,600, molecular weight distribution 1.2). Analysis ofthe functionalization rate of the obtained polyisobutylene was carriedout using NMR.

(NMR Method) Gemini-300 manufactured by Valian Inc.

Measurement solvent: a 4/1 mixed solvent of carbontetrachloride/deuterated acetone

Quantification method: The signal (4.00 ppm) of the methylene adjacentto the terminal hydroxyl group was compared with the standard signal(7.2 ppm) of the initiator residual group and quantified. Fn (CH₂OH)represents the introduction amount of functional groups on the polymerends. When functional groups are quantitatively introduced, Fn is 2.0for the initiator used in this example. The introduction amount ofhydroxyl groups of the polymer obtained in Comparative Example 4 is asfollows: Fn (CH₂OH)=1.90.

Next, a 200 ml separable flask was charged with 15.01 g (hydroxyl groupequivalent 5.1 mmol) of the polyisobutylene q-4 terminated with ahydroxyl group, and 30 ml of n-butyl chloride and 0.6 ml (7.6 mmol) ofpyridine that had been dehydrated with a molecular sieve 3A. A three-waycock, a thermocouple, and a stirring device equipped with a vacuum sealwas attached to the flask, and the flask was purged with nitrogen. Aftercooling to 0° C., 0.75 ml (7.6 mmol) of methacrylic acid chloride wasadded. The temperature was then raised to 23° C., and the mixture wasstirred for 2 hours. Since the reaction was not yet completed based onNMR, the mixture was cooled to 0° C., and then 0.5 ml (5.1 mmol) ofmethacrylic acid chloride and 0.4 ml (5.1 mmol) of pyridine were added.The temperature was then raised to 23° C., the mixture was stirred for 1hour, and the completion of the reaction was confirmed by NMR. Then, theproduct was washed four times with 200 ml of water, and reprecipitatedfrom methanol. The obtained liquid resin was removed by evaporationunder reduced pressure to obtain the target polyisobutylene Q-4terminated with a (meth)acryloyl group. The molecular weight of theobtained polymer Q-4 based on polystyrene was measured by size exclusionchromatography (SEC). Mw was 7,100, Mn was 5,900, and Mw/Mn was 1.20.Further, the Fn of the acryloyl groups introduced onto the end of theobtained acryloyl-terminated polyisobutylene Q-4 was 1.90.

To 100 parts by weight of the obtained acryloyl-terminatedpolyisobutylene Q-4 was added 2 parts of 2,2-diethoxyacetophenone(manufactured by Tokyo Chemical Industry Co., Ltd.) and thoroughlymixed. Then, this curable composition was poured into a metal frame (100mm×100 mm×0.5 mm) made of SUS304, and irradiated with light (lightamount 8,310 J/cm²) for 5 minutes using a high-pressure mercury lamp(SHL-100UVQ-2, manufactured by Toshiba Lighting & TechnologyCorporation) to obtain a cured product. The gel fraction, residualchlorine concentration, and gas permeability of the obtained curedproduct were evaluated. The results are shown in Table 1.

TABLE 1 Comparative Materials Example 5 Example 6 Example 7 Example 8Example 4 Polymer P-1 100 100 100 Polymer P-3 100 Polymer Q-4 100 Activeenergy ray Active energy ray polymerization 2.0 2.0 1.0 2.0polymerization initiator initiator mixture [1] 2,2-Diethoxyacetophenone2.0 Functionalization rate (Fn) of polymer 1.93 1.93 1.93 1.92 1.90Light amount (J/cm²) 2.6 1.0 2.6 2.6 8310 Gel fraction (%) 99 99 99 9699 Residual chlorine concentration (ppm) 85 85 85 79 9821 Gaspermeability Oxygen (10⁻¹⁶ mol · m/m² · sec · Pa) 4.4 4.6 4.7 4.4 4.5Water vapor (g/m² · 24H) 0.82 0.78 0.81 0.79 0.77 [1] Mixture ofDAROCURE 1173 (2-hydroxy-2-methyl-1-phenyl-propan-1-one, manufactured byCiba Japan K.K.) and IRGACURE 819(bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, manufactured by CibaJapan K.K.) at a weight ratio of 2/1

It can be seen that the chlorine atom content in the compositions andcured products shown in Examples 5 to 8 is much lower than inComparative Example 4. Further, it can also be seen that the time andthe light amount required for curing in Examples 5 to 8 is less than inComparative Example 4. Although the reasons for this are not clear, itis thought that atom structure near the terminal (meth)acryloyl group ofthe (meth)acryloyl-terminated polyisobutylene polymer used in thepresent invention has some sort of positive impact onphotopolymerizability.

Therefore, a composition characterized by containing the(meth)acryloyl-terminated polyisobutylene polymer according to thepresent invention can provide an excellent material that has a lowresidual halogen concentration and that can be thoroughly cured even byan irradiation of a small amount of light.

INDUSTRIAL APPLICABILITY

Since the active energy ray-curable composition and the cured productaccording to the present invention have a low halogen atom content andcan be rapidly cured by an irradiation of a small amount of light, theycan be used in various applications, such as for a sealing material, asealant, a coating material, a potting material, a fixed gasket, aformed-in-place gasket, an adhesive, a pressure-sensitive adhesive, afiller, a molding, a foam, a film, a casting material, an ink, ananti-vibration material, a damping material, a soundproofing material, aseismic isolation material and the like.

The invention claimed is:
 1. A (meth)acryloyl-terminated polyisobutylenepolymer represented by the following general formula (1):

wherein R¹ represents a divalent group that is dicumyl chloride with twochlorine atoms being removed; A represents a polyisobutylene polymer; R²represents a divalent saturated hydrocarbon group having 2 to 6 carbonatoms and containing no hetero atoms; R³ and R⁴ each represent hydrogen,a monovalent hydrocarbon group having 1 to 20 carbon atoms, or an alkoxygroup having 1 to 20 carbon atoms; R⁵ represents hydrogen or a methylgroup; and n is
 2. 2. The (meth)acryloyl-terminated polyisobutylenepolymer according to claim 1, wherein R² represents a divalenthydrocarbon group selected from the group consisting of —CH₂CH₂—,—CH₂CH₂CH₂—, —CH₂CH₂CH₂CH₂—, —CH₂CH₂CH₂CH₂CH₂—, and—CH₂CH₂CH₂CH₂CH₂CH₂—.
 3. The (meth)acryloyl-terminated polyisobutylenepolymer according to claim 1, wherein R² represents —CH₂CH₂—.
 4. The(meth)acryloyl-terminated polyisobutylene polymer according to claim 1,wherein R³ and R⁴ represent hydrogen.
 5. The (meth)acryloyl-terminatedpolyisobutylene polymer according to claim 1, wherein R⁵ representshydrogen.
 6. The (meth)acryloyl-terminated polyisobutylene polymeraccording to claim 1, wherein the (meth)acryloyl-terminatedpolyisobutylene polymer (A) has a molecular weight of 200 to 500,000 interms of number average molecular weight based on polystyrene measuredby size exclusion chromatography (SEC), and a molecular weightdistribution of 1.8 or less where the molecular weight distribution isrepresented by Mw/Mn, Mw/Mn is a ratio of the weight average molecularweight Mw to the number average molecular weight Mn.